Controlled release fertilizer material and process for production thereof

ABSTRACT

Thiol ester compositions, methods of making the thiol ester compositions, and methods of using the thiol ester compositions are provided. In some embodiments, the thiol ester compositions include thiol esters, hydroxy thiol esters and cross-linked thiol esters. The thiol ester composition can be used to produce cross-linked thiol esters, sulfonic acid-containing esters, sulfonate containing esters and thioacrylate containing esters. The thiol ester compositions can be used to produce polythiourethanes. The polythiourethanes can be used in fertilizers and fertilizer coatings.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of four provisional patentapplications having U.S. Ser. No. 60/545,260 filed on Feb. 17, 2004;U.S. Ser. No. 60/561,614 filed on Apr. 13, 2004; U.S. Ser. No.60/561,685 filed on Apr. 13, 2004; and U.S. Ser. No. 60/561,855 filed onApr. 13, 2004, which hereby are incorporated by reference in theirentirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to thiol containing ester compositions generallymade from a reaction of unsaturated ester compositions and a materialcapable of forming a thiol group. The invention also relates to theprocesses for preparing such thiol containing compositions and uses forthe thiol containing compositions.

2. Description of Related Art

The chemical industry strives to make products, such as polymers,fertilizers, and fuels, with less expensive feedstocks that are inabundant supply. As the fossil fuels slowly deplete over time,alternative sources are always being sought as replacements for fuels.Additionally, the chemical industry continuously strives to produceproducts and use feedstocks that are environmentally friendly in orderto reduce potential hazards and risks related to safety andenvironmental issues.

SUMMARY OF THE INVENTION

The present invention advantageously provides thiol containingcompositions and methods of making such compositions. In addition to thecompositions and methods of making such compositions, products thatinclude such compositions are also provided.

As an embodiment of the present invention, a thiol ester composition isadvantageously provided. In this embodiment, the thiol ester compositionincludes thiol ester molecules that have an average of at least 1.5ester groups per thiol ester molecule. The thiol ester molecules alsohave an average of at least 1.5 thiol groups per thiol ester molecule.The thiol ester molecules also have a molar ratio of cyclic sulfides tothiol groups of less than 1.5.

In some aspects, the thiol ester molecules have a molar ratio of cyclicsulfides to thiol groups ranging from 0 to 1.0. In some aspects, thethiol ester molecules have an average ranging from 1.5 to 9 thiol groupsper thiol ester molecule. In some embodiments, the thiol ester moleculeshave a molar ratio of carbon-carbon double bonds to thiol groups of lessthan 1.5.

The amount of thiol sulfur or mercaptan sulfur contained within thethiol ester molecules can also vary. For example, in some embodiments,the thiol ester molecules have an average of greater than 5 weightpercent thiol sulfur. In other embodiments, the thiol ester moleculeshave an average ranging from 8 to 10 weight percent thiol sulfur. Insome embodiments, the thiol ester molecules have an average of less than30 mole percent sulfur, which is present as cyclic sulfides.Alternatively, the thiol ester molecules have an average of less than 2mole percent sulfur present as cyclic sulfides.

In some embodiments, the thiol ester molecules are produced fromunsaturated esters that have an average of less than 25 weight percentof side chains that include 3 contiguous methylene interruptedcarbon-carbon double bonds. In another aspect, greater than 40 percentof the total side chains contained within the thiol ester moleculescontain sulfur.

In addition to the thiol ester composition, a process for producing thethiol ester composition is advantageously provided as another embodimentof the present invention. To produce the thiol ester composition,hydrogen sulfide is contacted with an unsaturated ester composition. Theunsaturated ester composition includes unsaturated esters that have anaverage of at least 1.5 ester groups per unsaturated ester molecule. Theunsaturated esters also have an average of at least 1.5 carbon-carbondouble bonds per unsaturated ester molecule. The hydrogen sulfide andthe unsaturated esters are reacted to produce or form the thiol estercomposition. The thiol ester composition advantageously includes thiolester molecules that have a molar ratio of cyclic sulfides to thiolgroups of less than 1.5.

Process variables related to the step of reacting the hydrogen sulfideand the unsaturated ester can be varied in embodiments in the presentinvention. In an aspect, the step of reacting the hydrogen sulfide andthe unsaturated esters occurs in the presence of a solvent. In anotheraspect, the step of reacting the hydrogen sulfide and the unsaturatedesters occurs in the substantial absence of a solvent. In someembodiments, the step of reacting the hydrogen sulfide and theunsaturated esters is catalyzed by a heterogeneous catalyst.Alternatively, the reaction of the hydrogen sulfide and the unsaturatedesters is initiated by a free-radical initiator or UV radiation. Thetemperature at which the hydrogen sulfide and the unsaturated ester arereacted can be varied. In some embodiments, reacting the hydrogensulfide and the unsaturated esters occurs at a temperature of greaterthan −20° C. As another example, the process is a continuous process andthe reaction of the hydrogen sulfide and the unsaturated esters isperformed in an absence of a solvent, at a temperature of greater than−20° C., and is initiated by UV radiation. Other types and combinationsof process variables can be changed in embodiments of the presentinvention, as will be understood by those of skill in the art.

Another process for producing the thiol ester composition isadvantageously provided as another embodiment of the present invention.In this process embodiment, the hydrogen sulfide and the unsaturatedester composition are contacted. The unsaturated ester compositionincludes unsaturated esters having an average of at least 1.5 estergroups per unsaturated ester molecule and having an average of at least1.5 carbon-carbon double bonds per unsaturated ester molecule. Thehydrogen sulfide and the unsaturated esters are then reacted in asubstantial absence of a solvent to form the thiol ester composition.The thiol ester composition includes thiol ester molecules. The thiolester composition advantageously includes thiol ester molecules thathave a molar ratio of cyclic sulfides to thiol groups of less than 1.5.

Process variables related to the step of reacting the hydrogen sulfideand the unsaturated ester can be varied in embodiments in the presentinvention. In an aspect, the step of reacting the hydrogen sulfide andthe unsaturated esters occurs in the presence of a solvent. In anotheraspect, the step of reacting the hydrogen sulfide and the unsaturatedesters occurs in the substantial absence of a solvent. In someembodiments, the step of reacting the hydrogen sulfide and theunsaturated esters is catalyzed by a heterogeneous catalyst.Alternatively, the reaction of the hydrogen sulfide and the unsaturatedesters is initiated by a free-radical initiator or UV radiation. Thetemperature at which the hydrogen sulfide and the unsaturated ester arereacted can be varied. In some embodiments, reacting the hydrogensulfide and the unsaturated esters occurs at a temperature of greaterthan −20° C.

In embodiments of the present invention, the unsaturated estercomposition includes a natural source oil, as described herein. In someembodiments, the unsaturated ester composition includes soybean oil.Other types of unsaturated ester compositions are described herein.

The resulting thiol ester molecules produced by this process possessadvantageous characteristics. For example, in some embodiments, thethiol ester molecules have a molar ratio of the hydrogen sulfide tocarbon-carbon double bonds of greater than 2. As another example, inother embodiments, the thiol ester molecules have an average of greaterthan 5 weight percent thiol sulfur. In some aspects, greater than 40percent of the thiol ester molecule total side chains contain sulfur.

As another embodiment of the present invention, another process forpreparing the thiol ester composition is advantageously provided. Inthis embodiment, a polyol composition and a thiol carboxylic acidcomposition are contacted and reacted to produce the thiol estercomposition. The thiol ester composition includes thiol ester moleculeshaving an average of at least 1.5 ester groups per thiol ester moleculeand having an average of at least 1.5 thiol groups per thiol estermolecule.

In addition to the thiol ester composition, other compositions areadvantageously provided as embodiments of the present invention. Forexample, a hydroxy thiol ester composition is provided as anotherembodiment of the present invention. The hydroxylthiol ester compositionincludes hydroxy thiol ester molecules having an average of at least 1.5ester groups per hydroxy thiol ester molecule and having an average ofat least 1.5 α-hydroxy thiol groups per hydroxy thiol ester molecule.

As described herein, the α-hydroxy thiol groups contain an alcohol orhydroxy group and a thiol group within the same group. In embodiments ofthe present invention, the α-hydroxy thiol groups can be replaced withseparate alcohol and thiol groups. In these embodiments, the same numberof α-hydroxy groups can be used for the separate alcohol and thiolgroups. For example, in some embodiments, the hydroxy thiol estermolecules have an average of at least 1.5 α-hydroxy thiol groups. Inembodiments that contain separate alcohol and thiol groups, the hydroxythiol ester molecules would contain an average of at least 1.5 alcoholgroups and an average of at least 1.5 thiol groups.

In some aspects, the hydroxy thiol ester molecules have an averageranging from 1.5 to 9 α-hydroxy thiol groups per hydroxy thiol estermolecule. In some embodiments, the thiol ester molecules have a molarratio of carbon-carbon double bonds to thiol groups of less than 1.5.

In some embodiments, the thiol ester molecules are produced fromunsaturated esters that have an average of less than 25 weight percentof side chains that include 3 contiguous methylene interruptedcarbon-carbon double bonds. In another aspect, greater than 40 percentof the total side chains contained within the α-hydroxy thiol estermolecules contain sulfur.

The amount of thiol sulfur contained within the hydroxy thiol estermolecules can also vary. For example, in some embodiments, the hydroxythiol ester molecules have an average of greater than 5 weight percentthiol sulfur. In other embodiments, the hydroxy thiol ester moleculeshave an average ranging from 8 to 10 weight percent thiol sulfur.

In some embodiments, the hydroxy thiol ester molecules have a molarratio of epoxide groups to the α-hydroxy thiol groups of less than 2. Inother aspects, the composition is substantially free of epoxide groups.

In addition to the hydroxy thiol ester composition, methods or processesfor making the hydroxy thiol ester composition are advantageouslyprovided as embodiments of the present invention. In an embodiment, aprocess for preparing the hydroxy thiol ester composition is providedthat includes the step of contacting the hydrogen sulfide and anepoxidized unsaturated ester composition. The epoxidized unsaturatedester composition includes epoxidized unsaturated esters having anaverage of at least 1.5 ester groups per epoxidized unsaturated estermolecule and having an average of at least 1.5 epoxide groups perepoxidized unsaturated ester molecule. The hydrogen sulfide and theepoxidized unsaturated esters are then reacted to form the hydroxy thiolester composition.

In embodiments of the present invention, the epoxidized unsaturatedester composition includes an epoxidized natural source oil, asdescribed herein. In some embodiments, the epoxidized unsaturated estercomposition includes an epoxidized soybean oil. Other types ofepoxidized unsaturated ester compositions are described herein.

In some embodiments, a molar ratio of the hydrogen sulfide to epoxidegroups in the epoxidized unsaturated esters is greater than 1.

In an aspect, the step of the hydrogen sulfide and the epoxidizedunsaturated esters is performed in the presence of a catalyst.

Another process for preparing the hydroxy thiol ester composition isadvantageously provided as another embodiment of the present invention.In this process embodiment, a polyol composition and a hydroxy thiolcarboxylic acid composition are contacted and reacted to produce thehydroxy thiol ester composition. In this embodiment, the hydroxy thiolester composition includes hydroxy thiol ester molecules having anaverage of at least 1.5 ester groups per hydroxy thiol ester moleculeand having an average of at least 1.5 α-hydroxy thiol groups per hydroxythiol ester molecule.

A cross-linked thiol ester composition is advantageously provided asanother embodiment of the present invention. The cross-linked thiolester composition includes thiol ester oligomers having at least twothiol ester monomers connected by a polysulfide linkage having astructure —S_(Q)—, wherein Q is greater than 1. In some embodiments, thethiol ester oligomers have at least three thiol ester monomers connectedby polysulfide linkages. In another aspect, the thiol ester oligomershave from 3 to 20 thiol ester monomers connected by polysulfidelinkages.

In an aspect, the cross-linked thiol ester composition includes boththiol ester monomers and thiol ester oligomers. In some embodiments, thethiol ester monomers and thiol ester oligomers have a total thiol sulfurcontent ranging from 0.5 to 8 weight percent; or alternatively, rangingfrom 8 to 15 weight percent. The combined thiol ester monomers and thiolester oligomers can have an average molecular weight greater than 2000;or alternatively, in a range from 2000 to 20,000.

As another embodiment of the present invention, a cross-linked thiolester composition produced by the process comprising the steps ofcontacting the thiol ester composition with an oxidizing agent andreacting the thiol ester and the oxidizing agent to form thiol esteroligomers is advantageously provided. In this embodiment, the thiolester oligomers have at least two thiol ester monomers connected by apolysulfide linkage having a structure —S_(Q)—, wherein Q is greaterthan 1.

A process to produce the cross-linked thiol ester composition is alsoadvantageously provided as another embodiment of the present invention.In this process, a thiol ester composition is contacted and reacted withan oxidizing agent to form thiol ester oligomers having at least twothiol ester monomers connected by a polysulfide linkage having astructure —S_(Q)—, wherein Q is greater than 1. In some embodiments, theoxidizing agent is elemental sulfur, oxygen, or hydrogen peroxide. In anaspect, the oxidizing agent is elemental sulfur.

In an aspect, the thiol ester is a hydroxy thiol ester. In otheraspects, a weight ratio of elemental sulfur to thiol sulfur in the thiolester molecules ranges from 0.5 to 32.

The step of the reacting the thiol ester and the oxidizing agent can beperformed at a temperature ranging from 25° C. to 150° C. The processfor producing the cross-linked thiol ester composition can also includethe step of stripping residual hydrogen sulfide from the cross-linkedthiol ester composition produced. In another aspect, the reaction of thethiol ester and the elemental sulfur is catalyzed. In some embodiments,the catalyst is an amine.

It is another object of the present invention to provide a novelfertilizer material.

It is another object of the present invention to provide a novel processfor production of a fertilizer material.

Accordingly, in one of its aspects, the present invention relates to anabrasion resistant polythiourethane and/or epoxy polymer encapsulatedcontrolled release fertilizer material.

In another of its aspects, the present invention relates to a controlledrelease fertilizer material comprising a particulate plant nutrientsurrounded by a coating which is the reaction product of a mixturecomprising: (i) a first component selected from an isocyanate and/or anepoxy resin, and (ii) a first active hydrogen-containing compoundselected from the group consisting of: a thiol ester composition; ahydroxy thiol ester composition; a cross-linked thiol ester compositionand mixtures thereof.

In another of its aspects, the present invention relates to a controlledrelease fertilizer material comprising a particulate plant nutrientsurrounded by a coating which is the reaction product of a mixturecomprising: (i) an isocyanate and/or an epoxy resin; and (ii) asulfur-containing vegetable oil.

In another of its aspects, the present invention relates to a controlledrelease fertilizer material comprising a particulate plant nutrientsurrounded by a coating which is the reaction product of a mixturecomprising: (i) an isocyanate and/or an epoxy resin, and (ii) asulfur-containing soybean oil.

In another of its aspects, the present invention relates to a controlledrelease fertilizer material comprising a particulate plant nutrientsurrounded by at least one coating comprising a polythiourethane and/oran epoxy polymer.

In another of its aspects, the present invention relates to a controlledrelease fertilizer material comprising a particulate plant nutrientsurrounded by at least one coating comprising the reaction product of amixture comprising an isocyanate, a wax and an activehydrogen-containing compound comprising a sulfur-containing vegetableoil.

In another of its aspects, the present invention relates to a processfor the production of abrasion resistant polythiourethane and/or epoxypolymer encapsulated controlled release fertilizer particles byincorporating in urethane and/or epoxy polymer forming reaction mixturea sulfur-containing compound such as one or more of a thiol estercomposition; a hydroxy thiol ester composition; a cross-linked thiolester composition, other sulfur-based compounds described herein belowand mixtures thereof.

Preferably, for the production of the present polythiourethaneencapsulated controlled release fertilizer material, a sulfur-containingcompound (e.g., one or more of a thiol ester composition; a hydroxythiol ester composition; a cross-linked thiol ester composition) is usedas one of the isocyanate-reactive components (alone or in combinationwith other active hydrogen-containing compounds). Preferably, thesulfur-containing compound comprises a sulfur-containing vegetable oil.In one preferred embodiment, the sulfur-containing vegetable oilcomprises a mercaptanized vegetable oil (MVO), more preferably asdescribed in more detail herein, even more preferably an MVO produced bythe addition of hydrogen sulfide to a vegetable oil. In anotherpreferred embodiment, the sulfur-containing vegetable oil comprisesmercapto-hydroxy vegetable oil (MHVO), more preferably as described inmore detail herein, even more preferably an MHVO produced by theaddition of hydrogen sulfide to epoxidized vegetable oil. In yet anotherpreferred embodiment, the sulfur containing vegetable oil comprisessulfur cross-linked mercaptanized vegetable oil (CMVO), more preferablyas described in more detail herein, even more preferably an CMVOproduced by the addition of elemental sulfur to mercaptanized vegetableoil (MVO).

Preferably, for the production of epoxy polymer encapsulated controlledrelease fertilizer material, a sulfur-containing compound (e.g., one ormore of a thiol ester composition; a hydroxy thiol ester composition; across-linked thiol ester composition) is used as one of theisocyanate-reactive components (alone or in combination with otheractive hydrogen-containing compounds). Preferably, the sulfur-containingcompound comprises a sulfur-containing vegetable oil (e.g., MVO and/orMHVO and/or CMVO) is used as one of the epoxy resin-reactive components.

In one preferred embodiment of the present process, a polythiourethaneencapsulated controlled release fertilizer material is produced byemploying the following steps:

(i) applying an isocyanate-reactive component comprising asulfur-containing vegetable oil (preferably one or more of MVO, MHVO andCMVO described herein) to fertilizer particles to form coated fertilizerparticles, and

(ii) applying an isocyanate to the coated fertilizer particles to formthe fertilizer material.

Steps (i) and (ii) are optionally repeated successively a number oftimes (e.g., 2-10) to form a desired thickness of the polythiourethanecoating which encapsulates the fertilizer particles. The controlledrelease fertilizer material produced by this process preferably containsfrom about 1.5 to 20% by weight, more preferably from about 2 to 15% byweight, most preferably from about 2.5 to 10% by weight, ofpolythiourethane coating, based upon the total weight of the coatedfertilizer material.

In another embodiment, a polythiourethane encapsulated controlledrelease fertilizer material is produced by employing the followingsteps:

(i) applying an isocyanate component to fertilizer particles to formcoated fertilizer particles, and

(ii) applying an active hydrogen-containing compound comprising asulfur-containing vegetable oil (preferably one or more of MVO, MHVO andCMVO described herein) to the coated fertilizer particles to form thefertilizer material.

Again, Steps (i) and (ii) are optionally repeated successively a numberof times (e.g., 2-10) to form a desired thickness of thepolythiourethane coating which encapsulates the fertilizer particles.The controlled release fertilizer material produced by this processpreferably contains from about 1.5 to 20% by weight, more preferablyfrom about 2 to 15% by weight, most preferably from about 2.5 to 10% byweight, of polythiourethane coating, based upon the total weight of thecoated fertilizer material.

In yet a further embodiment, a polythiourethane encapsulated controlledrelease fertilizer material is produced by employing the followingsteps:

(i) applying to fertilizer particles a prepolymer of an isocyanate andan active hydrogen-containing compound comprising a sulfur-containingvegetable oil (preferably one or more of MVO, MHVO and CMVO describedherein) to form coated fertilizer particle to form the fertilizermaterial;

(ii) converting the prepolymer to a polythiourethane to form thefertilizer material.

The prepolymer used in Step (i) may be produced by contacting: (a) anactive hydrogen-containing compound comprising a sulfur-containingvegetable oil (preferably one or more of MvO, MHVO and CMVO describedherein) and (b) an isocyanate to produce a prepolymer eithercontinuously or in a batch process in quantities such that the ratio offree (i.e., unreacted) isocyanate groups contained in component (b) tofree (i.e., unreacted) active hydrogen moieties in component (a) is fromabout 0.8:1 to about 2.0:1, preferably from about 0.9:1 to about 1.5:1,more preferably from about 0.95:1 to about 1.3:1.

Thus, in one embodiment, the prepolymer used in Step (i) has excessisocyanate groups. In this case, the conversion in Step (ii) comprisesadding further active hydrogen-containing compound which is the same ordifferent than that used in Step (i). In another embodiment, theprepolymer used in Step (i) has excess active hydrogen groups. In thiscase, the conversion in Step (ii) comprises adding further isocyanatewhich is the same or different than that used in Step (i). It ispreferred that Step (ii) comprises addition of sufficient activehydrogen-containing compound or isocyanate (as the case may be) tocompensate for substantially all free isocyanate or active hydrogenreactive groups on the prepolymer.

The embodiment involving prepolymers should be conducted carefullysince, once the co-reactants are mixed together the reaction starts toform polythiourethane and the viscosity of the mixture increases, whichcan reduce the spreadability of the components over the fertilizerparticles. However, this viscosity increase can be managed by limitingthe mixing time and temperature of the co-reactants prior to beingapplied to the fertilizer particles.

In a further preferred embodiment, organic additives can be: (1) addedto one or more of the co-reactants (premix) and/or (2) first applied tothe fertilizer particles prior to the co-reactants (precoat) and/or 3)applied to the polythiourethane coated fertilizer particles as a laststep (overcoat). Non-limiting examples of suitable organic additives maybe selected from the group comprising waxes, petrolatums, asphalts,fatty acids, fatty acid salts, fatty acid esters, higher alcohols,silicones and mixtures thereof.

In addition, the coating formulation may contain cross-linking agents,commonly used by those skilled in the art of producing polyurethanepolymers. Suitable cross-linking agents may be selected from the groupcomprising low molecular weight diols, amine initiated polyethylene andpolypropylene glycols, glycerol, sorbitol, neopentyl glycol, alkyldiamines, aryldiammines and mixtures thereof.

In addition the use of catalysts, commonly used for the polyurethaneproduction, can be used in the present process to increase the rate ofcure of the polythiourethane coating. Suitable catalysts may be selectedfrom the group comprising tertiary amines, organo-tin compounds andmixtures thereof.

Optionally, other additives for increasing flowability and/orspreadability of the coating materials can be used in the presentprocess. These include flow and spread agents conventionally used bythose skilled in the art of polyurethane production.

In a preferred embodiment, the process for producing epoxy polymerencapsulated controlled release fertilizer material comprises thefollowing steps:

(i) applying an epoxy-reactive component comprising a sulfur-containingvegetable oil (preferably one or more of MVO, MHVO and CMVO describedherein) to fertilizer particles to form coated fertilizer particles; and

(ii) applying an epoxy resin component to the coated fertilizerparticles to the fertilizer material.

Steps (i) and (ii) are optionally repeated successively a number oftimes (e.g., 2-10) to form a desired thickness of the epoxy polymercoating which encapsulates the fertilizer particles. The controlledrelease fertilizer material produced by this process preferably containsfrom about 1.5 to 20% by weight, more preferably from about 2 to 15% byweight, most preferably from about 2.5 to 10% by weight, of epoxypolymer coating, based upon the total weight of the coated fertilizermaterial.

For epoxy polymers produced from mercaptanized vegetable oils it hasbeen found that the use of a tertiary amine catalyst is highlypreferred. The amine catalyst forms the mercaptide anion of themercaptanized vegetable oil. It is the mercaptide anion form of themercaptanized vegetable oil that is reactive with epoxy resins, asdescribed by Wicks, Z. W. et al in “Organic Coatings: Science andTechnology”, Vol. 1, John Wiley & Sons, 1992, p. 179.

The present invention also relates to encapsulated fertilizercompositions produced by these processes.

The preferred sulfur-containing vegetable oils useful in the aspects ofthe invention relating to fertilizer material are those discussed inmore detail herein. A particularly preferred sulfur-containing vegetableoil is Polymercaptan 358 available from Chevron Phillips Chemical Co.and which is the reaction product of soybean oil and hydrogen sulfide.

It has been surprisingly and unexpectedly discovered that that improvedcontrolled (e.g., slow) release fertilizer material can be produced whena sulfur-containing vegetable oil is used as an isocyanate-reactivecomponent for forming polythiourethane encapsulated fertilizer material.Further, it has been surprisingly and unexpectedly discovered that thatimproved controlled (e.g., slow) release fertilizer material can beproduced when a sulfur-containing vegetable oil is used in theepoxy-reactive component for forming epoxy polymer encapsulatedfertilizer material. The use of such a sulfur-containing vegetable oilresults in a number of advantages, including: the resulting fertilizermaterial as improved resistance to abrasion (i.e., it has improveddurability during production and/or handling); the sulfur-containingvegetable oil is derived from a natural, renewable resource materials;the sulfur-containing vegetable oil has increased hydrophobicity due tothe sulfur content compared with conventional polyols which contain morepolar oxygen functional groups; and it is possible to achieve aprescribed release rate profile for a fertilizer material using lowercoat weights (e.g., as compared to those described in U.S. Pat. No.5,538,531 [Hudson] and U.S. Pat. No. 6,358,296 [Markusch]) therebysignificantly reducing the cost of produce the finished fertilizermaterial.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the features, advantages and objects of theinvention, as well as others that will become apparent, can beunderstood in more detail, more particular description of the inventionbriefly summarized above can be had by reference to the embodimentthereof that is illustrated in the appended drawings, which form a partof this specification. It is to be noted, however, that the drawingsillustrate only particular embodiments of the invention and aretherefore not to be considered limiting of the invention's scope as itmay admit to other equally effective embodiments.

FIG. 1 includes two graphs that compare the NMR's of soybean oil, whichis shown in the top graph, and a thiol containing ester produced fromsoybean oil in accordance with an embodiment of the present invention,which is shown in the bottom graph;

FIG. 2 includes two graphs that compare the NMR's of epoxidized soybeanoil, which is shown in the top graph, and a thiol containing esterproduced from epoxidized soybean oil in accordance with an embodiment ofthe present invention, which is shown in the bottom graph;

FIG. 3 is a gas chromatograph (GC)/mass spectrometer (MS) trace of athiol containing ester that was produced from soybean oil in accordancewith an embodiment of the present invention and then treated bymethanolysis;

FIG. 4 is a GC/MS trace of epoxidized soybean oil treated bymethanolysis;

FIG. 5 is a GC/MS trace of hydroxy thiol containing ester produced fromepoxidized soybean oil in accordance with an embodiment of the presentinvention and then treated by methanolysis;

FIGS. 6A-6F are tables that contain physical property data for numerouspolythiourethane compositions prepared in accordance with embodiments ofthe present invention;

FIG. 7 illustrates the water release performance of a CRF materialproduced in Fertilizer Examples 1-3 in accordance with an embodiment ofthe present invention;

FIG. 8 illustrates the water release performance of a CRF materialproduced in Fertilizer Examples 4-6 in accordance with an embodiment ofthe present invention;

FIG. 9 illustrates the water release performance of a CRF materialproduced in Fertilizer Examples 7-10 in accordance with an embodiment ofthe present invention;

FIG. 10 illustrates the water release performance of a CRF materialproduced in Fertilizer Examples 11-14 in accordance with an embodimentof the present invention; and

FIG. 11 illustrates the water release performance of a CRF materialproduced in Fertilizer Examples 15-17 in accordance with an embodimentof the present invention.

DETAILED DESCRIPTION OF THE INVENTION

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or “approximate”is used in connection therewith. They can vary by 1%, 2%, 5%, andsometimes, 10 to 20%. Whenever a numerical range with a lower limit,R_(L) and an upper limit, R_(U), is disclosed, any number falling withinthe range is specifically disclosed. In particular, the followingnumbers within the range are specifically disclosed:R=R_(L)+k*(R_(U)−R_(L)), wherein k is a variable ranging from 1% to 100%with a 1% increment, i.e., k is 1%, 2%, 3%, 4%, 5%, . . . , 50%, 51%,52%, . . . , 95%, 96%, 97%, 98%, 99%, or 100%. Moreover, any numericalrange defined by two R numbers as defined in the above is alsospecifically disclosed.

In this specification “natural” refers to materials obtained, by anymethod, from naturally occurring fruits, nuts, vegetables, plants andanimals. As an example, natural source oil refers to source oilsextracted, and optionally purified, from naturally occurring fruits,nuts, vegetables, plants and animals. Additionally, unsaturated naturalsource oil refers to unsaturated source oils extracted, and optionallypurified, from naturally occurring fruits, nuts, vegetables, plants, andanimals.

In this specification, “natural source raw material” refers to materialsobtained by extraction, chemical breakdown, or chemical processing of“natural” materials. A nonlimiting example includes natural source oilsthat can be extracted from naturally occurring fruits, nuts, vegetables,plants and animals. As another non-limiting example, glycerol andcarboxylic acids or carboxylic acid esters, saturated or unsaturated,can be produced and isolated by the chemical processing of triglyceridesextracted from naturally occurring fruits, nuts, vegetables, plants, andanimals.

In this specification “synthetic” refers to materials produced fromchemical building blocks not directly derived from natural sources. Forexample synthetic unsaturated ester oil can be produced by the reactionof synthetic ethylene glycol and a synthetic carboxylic acid, i.e.acrylic acid or propionic acid. Other types of synthetic materials willbe apparent to those of skill in the art and are to be considered withinthe scope of the present invention.

Regardless of the definitions of natural and synthetic, the materialsdescribed herein can be produced from a combination of natural andsynthetic materials, “semi-synthetic”. As a non-limiting example, theunsaturated ester oils described in this specification can be obtainedor produced from a combination of synthetic and natural source rawmaterials. For example, the unsaturated ester oil can be produced by thereaction of synthetic ethylene glycerol and oleic acid isolated from anatural source oil. Alternatively, the unsaturated ester oil can beproduced from the reaction of glycerol isolated from natural source oilsand a synthetic carboxylic acid, i.e. acrylic acid. Alternatively, theunsaturated ester oil can be produced from glycerol and oleic acidisolated from natural source oils.

In this specification, “thiol ester composition” refers to an estercomposition that includes “thiol ester molecules.” The thiol estermolecule has at least one thiol group and at least one ester groupwithin the thiol ester molecule.

In this specification, “hydroxy thiol ester composition” refers to anester composition that includes “hydroxy thiol ester molecules.” Thehydroxy thiol ester molecule has at least one thiol group, at least oneester group, and at least one hydroxy or alcohol group within thehydroxy thiol ester molecule. Alternatively, the alcohol group and thethiol group can be combined in the same group, which is referred to asan “α-hydroxy thiol group.”

In this specification, “sulfonic acid-containing ester composition”refers to a composition that includes sulfonic acid-containing estermolecules. The sulfonic acid-containing ester molecules have at leastone sulfonic acid group and at least one ester group within the sulfonicacid-containing ester molecule.

In this specification, “sulfonate-containing ester composition” refersto an ester composition that includes sulfonate-containing estermolecules. The sulfonate-containing ester molecules have at least onesulfonate group and at least one ester group within thesulfonate-containing ester molecule.

In this specification, “unsaturated ester composition” refers to anester composition that includes unsaturated ester molecules. Theunsaturated ester molecules have at least one ester group and at leastone carbon-carbon double bond within the sulfonate-containing estermolecule.

In this specification, “epoxidized unsaturated ester composition” refersto an ester composition that has been produced by epoxidizing anunsaturated ester composition.

In this specification, “polythiourethane” refers to a urethanecomposition that includes more than one of the following structure:

The presence of the thiourethane group can be determined by method knownto those skilled in the art (for example infrared spectroscopy, Ramanspectroscopy, and/or NMR).Thiol Ester Composition

The present invention advantageously provides a thiol ester compositionas an embodiment of the present invention. The thiol ester compositionincludes thiol ester molecules that have an average of at least 1.5ester groups and an average of at least 1.5 thiol groups per thiol estermolecule. The thiol ester composition also has a molar ratio of cyclicsulfides to thiol groups of less than 1.5, as described herein.

Generally, the thiol ester composition contains molecules having atleast one ester group and at least one thiol group. The thiol estercomposition of this invention can be produced from any unsaturatedester, as described herein. Because the feedstock unsaturated esters cancontain multiple carbon-carbon double bonds per unsaturated estermolecule, carbon-carbon double bond reactivity and statisticalprobability dictate that each thiol ester molecule of the thiol estercomposition produced from the unsaturated ester composition will nothave the same number of thiol groups, number of unreacted carbon-carbondouble bonds, number of cyclic sulfides, molar ratio of carbon-carbondouble bonds to thiol groups, molar ratio of cyclic sulfides to thiolgroups and other quantities of functional groups and molar ratiosdisclosed herein as the feedstock unsaturated ester. Additionally, thefeedstock unsaturated esters can also comprise a mixture of individualunsaturated esters having a different number of carbon-carbon doublebonds and/or ester groups. Thus, many of these properties will bediscussed as an average number of the groups per thiol ester moleculewithin the thiol ester composition or average ratio per thiol estermolecule within the thiol ester composition. In other embodiments, it isdesired to control the content of thiol sulfur present in the thiolester. Because it is difficult to ensure that the hydrogen sulfidereacts with every carbon-carbon double bond within the unsaturatedester, certain molecules of thiol ester can have more or less thiolgroups than other molecules. Thus, the weight percent of thiol groups isstated as an average across all thiol ester molecules of the thiol estercomposition.

The thiol ester can be derived from any unsaturated ester describedherein.

The thiol ester compositions can be described as comprising one or moreseparate or discreet functional groups of the thiol ester moleculeand/or thiol ester composition. These independent functional groups caninclude: the number of (or average number of) ester groups per thiolester molecule, thiol containing the number of (or average number of)thiol groups per thiol ester molecule, the number of (or average numberof) unreacted carbon-carbon double bonds per thiol ester molecule, theaverage thiol sulfur content of the thiol ester composition, thepercentage (or average percentage) of sulfide linkages per thiol estermolecule, and the percentage (or average percentage) of cyclic sulfidegroups per thiol ester molecule. Additionally, the thiol estercompositions can be described using individual or a combination ofratios including the ratio of double bonds to thiol groups, the ratio ofcyclic sulfides to mercaptan group, and the like. As separate elements,these functional groups of the thiol composition will be describedseparately.

Minimally, in some embodiments, the thiol ester contains thiol estermolecules having at least one ester group and one thiol group per thiolester molecule. As the thiol ester is prepared from unsaturated esters,the thiol ester can contain the same number of ester groups as theunsaturated esters described herein. In an embodiment, the thiol estermolecules have an average of at least 1.5 ester groups per thiol estermolecule. Alternatively, the thiol ester molecules have an average of atleast 2 ester groups per thiol ester molecule; alternatively, an averageof at least 2.5 ester groups per thiol ester molecule; or alternatively,an average of at least 3 ester groups per thiol ester molecule. In otherembodiments, the thiol esters have an average of from 1.5 to 8 estergroups per thiol ester molecule; alternatively, an average of from 2 to7 ester groups per thiol ester molecule; alternatively, an average offrom 2.5 to 5 ester groups per thiol ester molecule; or alternatively,an average of from 3 to 4 ester groups per thiol ester molecule. In yetother embodiments, the thiol ester comprises an average of 3 estergroups per thiol ester molecule or alternatively, an average of 4 estergroups per unsaturated ester molecule.

Minimally, the thiol ester comprises an average of at least one thiolgroup per thiol ester molecule. In an embodiment, the thiol estermolecules have an average of at least 1.5 thiol groups per thiol estermolecule; alternatively, thiol containing an average of at least 2 thiolgroups per thiol ester molecule; alternatively, an average of at least2.5 thiol groups per thiol ester molecule; or alternatively, an averageof at least 3 thiol groups per thiol ester molecule. In otherembodiments, the thiol ester molecules have an average of from 1.5 to 9thiol groups per thiol ester molecule; alternatively, an average of from3 to 8 thiol groups per thiol ester molecule; alternatively, thiolcontaining an average of from 2 to 4 thiol groups per thiol estermolecule, or alternatively, an average of from 4 to 8 thiol groups perthiol ester molecule.

In other embodiments, the thiol ester can be described by the averageamount of thiol sulfur present in thiol ester. In an embodiment, thethiol ester molecules have an average of at least 5 weight percent thiolsulfur per thiol ester molecule; alternatively, an average of at least10 weight percent thiol sulfur per thiol ester molecule, oralternatively, an average of greater than 15 weight percent thiol sulfurper thiol ester molecule. In an embodiment, the thiol ester moleculeshave an average of from 5 to 25 weight percent thiol sulfur per thiolester molecule; alternatively, an average of from 5 to 20 weight percentthiol sulfur per thiol ester molecule; alternatively, an average of from6 to 15 weight percent thiol sulfur per thiol ester molecule; oralternatively, an average of from 8 to 10 weight percent thiol sulfurper thiol ester molecule.

Generally, the location of the thiol group of the thiol ester is notparticularly important and will be dictated by the method used toproduce the thiol ester. In embodiments wherein the thiol ester isproduced by contacting an unsaturated ester, the position of the thiolgroup will be dictated by the position of the carbon-carbon double bond.When the carbon-carbon double bond is an internal carbon-carbon doublebond, the method of producing the thiol ester will result in a secondarythiol group. However, when the double bond is located at a terminalposition it is possible to choose reaction conditions to produce a thiolester comprising either a primary thiol group or a secondary thiolgroup.

Some methods of producing the thiol ester composition can additionallycreate sulfur containing functional groups other than a thiol group. Forexample, in some thiol ester production methods, an introduced thiolgroup can react with a carbon-carbon double bond within the sameunsaturated ester to produce a sulfide linkage. When the reaction iswith a double bond of a second unsaturated ester, this produces a simplesulfide linkage. However, in some instances, the second carbon-carbondouble bond is located in the same unsaturated ester molecule. When thethiol group reacts with a second carbon-carbon double bond within thesame unsaturated ester molecule, a sulfide linkage is produced. In someinstances, the carbon-carbon double bond can be within a second estergroup of the unsaturated ester molecule. While in other instances, thecarbon-carbon double bond can be within the same ester group of theunsaturated ester molecule.

When the thiol group reacts with the carbon-carbon double bond in asecond ester group of the same unsaturated ester molecule, the cyclicsulfide would contain two ester groups contained within a ringstructure. When the thiol group reacts with the carbon-carbon doublebond within the same ester group, the cyclic sulfide would not containan ester group within the ring structure. Within this specification,this second type of cyclic sulfide is referred to as a cyclic sulfide.Within this specification, the first type of cyclic sulfide is referredto as a simple sulfide. In the cyclic sulfide case, the sulfide linkageproduces a cyclic sulfide functionality within a single ester group ofthe thiol ester. This linkage is termed a cyclic sulfide for purposes ofthis application. One such sulfide group that can be produced is acyclic sulfide. The cyclic sulfide rings that can be produced include atetrahydrothiopyran ring, a thietane ring, or a thiophane ring(tetrahydrothiophene ring).

In some embodiments, it is desirable to control the average amount ofsulfur present as cyclic sulfide in the thiol ester. In an embodimentthe average amount of sulfur present as cyclic sulfide in the thiolester molecules comprises less than 30 mole percent. Alternatively, theaverage amount of sulfur present as cyclic sulfide in the thiol esterscomprises less than 20 mole percent; alternatively, less than 10 molepercent; alternatively, less than 5 mole percent; or alternatively, lessthan 2 mole percent. In other embodiments, it is desired to control themolar ratio of cyclic sulfides to thiol groups. In other embodiments, itis desirable to have molar ratios of cyclic sulfide to thiol group. Inan embodiment, the average molar ratio of cyclic sulfide groups to thiolgroup per thiol ester is less than 1.5. Alternatively, the average molarratio of cyclic sulfide groups to thiol group per thiol ester is lessthan 1; alternatively, less than 0.5; alternatively, less than 0.25; oralternatively, 0.1. In some embodiments, the ratio of cyclic sulfidegroups to thiol group per thiol ester ranges from 0 to 1; oralternatively, the average molar ratio of cyclic sulfide groups to thiolgroup per thiol ester ranges between 0.05 and 1.

In some instances it can desirable to have carbon-carbon double bondspresent in the thiol ester composition while in other embodiments it canbe desirable to minimize the number of carbon-carbon double bondspresent in the thiol ester composition. The presence of carbon-carbondouble bonds present in the thiol ester can be stated as an averagemolar ratio of carbon-carbon double bonds to thiol-sulfur. In anembodiment, the average ratio of the remaining unreacted carbon-carbondouble bond in the thiol ester composition to thiol sulfur is less than1.5 per thiol ester molecule. Alternatively, the average ratio ofcarbon-carbon double bond to thiol sulfur is less than 1.2 per thiolester molecule; alternatively, less than 1.0 per thiol ester molecule;alternatively, less than 0.75 per thiol ester molecule; alternatively,less than 0.5 per thiol ester molecule; alternatively, less than 0.2 perthiol ester molecule; or alternatively, less than 0.1 per thiol estermolecule.

In particular embodiments, the thiol ester is produced from unsaturatedester compositions. Because the feedstock unsaturated ester hasparticular compositions having a certain number of ester groups present,the product thiol ester composition will have about the same number ofester groups per thiol ester molecule as the feedstock unsaturatedester. Other, independent thiol ester properties described herein can beused to further describe the thiol ester composition.

In some embodiments, the thiol ester molecules are produced fromunsaturated esters having an average of less than 25 weight percent ofside chains having 3 contiguous methylene interrupted carbon-carbondouble bonds, as described herein. In some embodiments, greater than 40percent of the thiol containing natural source total side chains caninclude sulfur. In some embodiments, greater than 60 percent of thethiol ester molecule total side chains can include sulfur. In otherembodiments, greater than 50, 70, or 80 percent of the thiol estermolecule total side chains can include sulfur.

In an embodiment, the thiol ester is a thiol containing natural sourceoil, as described herein. When the thiol ester is a thiol containingnatural source oil, functional groups that are present in the thiolcontaining natural source oil can be described in a “per thiol estermolecule” basis or in a “per triglyceride” basis. The thiol containingnatural source oil can have substantially the same properties as thethiol ester composition, such as the molar ratios and other independentdescriptive elements described herein.

The average number of thiol groups per triglyceride in the thiolcontaining natural source oil is greater than about 1.5. In someembodiments, the average number of thiol groups per triglyceride canrange from about 1.5 to about 9.

The thiol ester compositions can also be described as a product producedby the process comprising contacting hydrogen sulfide and an unsaturatedester composition and can be further limited by the process as describedherein. The thiol containing natural source oil can also be describedusing a molecular weight or an average molecular weight of the sidechains.

Hydroxy Thiol Ester Composition

In embodiments of the present invention, the thiol ester compositionscan also contain a hydroxy or alcohol group. When the thiol estercomposition includes the hydroxy group, the thiol ester composition isreferred to herein as the hydroxy thiol ester composition. The quantityor number of alcohol groups present in the hydroxy thiol estercomposition can be independent of the quantity of other functionalgroups present in the hydroxy thiol ester composition (i.e. thiolgroups, ester groups, sulfides, cyclic sulfides). Additionally, theweight percent of thiol sulfur and functional group ratios (i.e. molarratio of cyclic sulfides to thiol groups, molar ratio of epoxide groupsto thiol groups, molar ratio of epoxide groups to α-hydroxy thiol groupsand other disclosed quantities of functional groups and their molarratios to the thiol groups) are separate or discreet elements that canbe used to describe the hydroxy thiol ester composition. The hydroxythiol ester composition can be described using any combination of thehydroxy thiol ester composition separate functional groups or ratiosdescribed herein.

In an embodiment, the hydroxy thiol ester composition is produced byreacting hydrogen sulfide with an epoxidized unsaturated estercomposition as described herein. Because the epoxidized unsaturatedester can contain multiple epoxide groups, epoxide group reactivity andstatistical probability dictate that not all hydroxy thiol estermolecules of the hydroxy thiol ester composition will have the samenumber of hydroxy groups, thiol groups, α-hydroxy thiol groups,sulfides, cyclic sulfides, molar ratio of cyclic sulfides to thiolgroups, molar ratio of epoxide groups to thiol groups, molar ratio ofepoxide groups to α-hydroxy thiol groups, weight percent thiol sulfurand other disclosed quantities of functional groups and their molarratios as the epoxidized unsaturated ester composition. Thus, many ofthese properties will be discussed as an average number or ratio perhydroxy thiol ester molecule. In other embodiments, it is desired tocontrol the content of thiol sulfur present in the hydroxy thiol ester.Because it is difficult to ensure that the hydrogen sulfide reacts withevery epoxide group within the epoxidized unsaturated ester, certainhydroxy thiol ester molecules can have more or less thiol groups thanother molecules within the hydroxy thiol ester composition. Thus, theweight percent of thiol groups can be stated as an average weightpercent across all hydroxy thiol ester molecules.

As an embodiment of the present invention, the hydroxy thiol estercomposition includes hydroxy thiol ester molecules that have an averageof at least 1 ester groups and an average of at least 1 α-hydroxy thiolgroups per hydroxy thiol ester molecule. As an embodiment of the presentinvention, the hydroxy thiol ester composition includes hydroxy thiolester molecules that have an average of at least 1.5 ester groups and anaverage of at least 1.5 α-hydroxy thiol groups per hydroxy thiol estermolecule.

Minimally, in some embodiments, the hydroxy thiol ester comprises atleast one ester, at least one thiol group, and at least one hydroxygroup. Because the hydroxy thiol ester is prepared from epoxidizedunsaturated esters, the hydroxy thiol ester can contain the same numberof ester groups as the epoxidized unsaturated esters. In an embodiment,the hydroxy thiol ester molecules have an average of at least 1.5 estergroups per hydroxy thiol ester molecule. Alternatively, the hydroxythiol ester molecules have an average of at least 2 ester groups perhydroxy thiol ester molecule; alternatively, an average of at least 2.5ester groups per hydroxy thiol ester molecule; or alternatively, anaverage of at least 3 ester groups per hydroxy thiol ester molecule. Inother embodiments, the hydroxy thiol esters have an average of from 1.5to 8 ester groups per hydroxy thiol ester molecule; alternatively, anaverage of from 2 to 7 ester groups per hydroxy thiol ester molecule;alternatively, an average of from 2.5 to 5 ester groups per hydroxythiol ester molecule; or alternatively, an average of from 3 to 4 estergroups per hydroxy thiol ester molecule. In yet other embodiments, theα-hydroxy thiol ester comprises an average of 3 ester groups per hydroxythiol ester molecule or alternatively, an average of 4 ester groups perhydroxy thiol ester molecule.

In some embodiments, the hydroxy group and the thiol group are combinedin the same group, which produces the α-hydroxy thiol group. In otherembodiments, the thiol group and the hydroxy or alcohol group are not inthe same group. When this occurs, to produce the hydroxy thiol estercomposition, the alcohol group is added independently of the thiolgroup. For example, as another embodiment of the present invention, thehydroxy thiol ester composition advantageously includes hydroxy thiolester molecules. The hydroxy thiol ester molecules have an average of atleast 1.5 ester groups, an average of at least 1.5 thiol groups, and anaverage of at least 1.5 alcohol groups per hydroxy thiol ester molecule.

Minimally, in some embodiments, the hydroxy thiol ester comprises atleast one thiol group per hydroxy thiol ester molecule. In anembodiment, the hydroxy thiol ester molecules have an average of atleast 1.5 thiol groups per hydroxy thiol ester molecule; alternatively,an average of at least 2 thiol groups per hydroxy thiol ester molecule;alternatively, an average of at least 2.5 thiol groups per hydroxy thiolester molecule; or alternatively, an average of at least 3 thiol groupsper hydroxy thiol ester molecule. In other embodiments, the hydroxythiol ester molecules have an average of from 1.5 to 9 thiol groups perhydroxy thiol ester molecule; alternatively, an average of from 3 to 8thiol groups per hydroxy thiol ester molecule; alternatively, an averageof from 2 to 4 thiol groups per hydroxy thiol ester molecule; oralternatively, an average of from 4 to 8 thiol groups per hydroxy thiolester.

Minimally, in some embodiments, the hydroxy thiol ester compositioncomprises an average of at least 1 hydroxy or alcohol group per hydroxythiol ester molecule. In some embodiments, the hydroxy thiol estercomposition comprises an average of at least 1.5 hydroxy groups perhydroxy thiol ester molecule; alternatively, average of at least 2hydroxy groups per hydroxy thiol ester molecule; alternatively, anaverage of at least 2.5 hydroxy groups per hydroxy thiol ester molecule;or alternatively, an average of at least 3 hydroxy groups per thiolester molecule. In other embodiments, the thiol ester compositioncomprises an average of from 1.5 to 9 hydroxy groups per hydroxy thiolester molecule; alternatively, an average of from 3 to 8 hydroxy groupsper hydroxy thiol ester molecule; alternatively, an average of from 2 to4 hydroxy groups per hydroxy thiol ester molecule; or alternatively, anaverage of from 4 to 8 hydroxy groups per hydroxy thiol ester molecule.

In yet other embodiments, the number of hydroxy groups can be stated asan average molar ratio of hydroxy group to thiol groups. Minimally, insome embodiments, the molar ratio of hydroxy groups to thiol groups isat least 0.25. In some embodiments, the molar ratio of hydroxy groups tothiol groups is at least 0.5; alternatively, at least 0.75;alternatively, at least 1.0; alternatively, at least 1.25; oralternatively, at least 1.5. In other embodiments, the molar ratio ofhydroxy groups to thiol groups ranges from 0.25 to 2.0; alternatively,from 0.5 to 1.5; or alternatively, from 0.75 to 1.25.

In embodiments where the hydroxy thiol esters are produced from anepoxidized unsaturated ester, the hydroxy thiol esters can be describedas containing ester groups and α-hydroxy thiol groups. The number ofester groups and the number of α-hydroxy thiol groups are independentelements and as such the hydroxy thiol esters can be described as havingany combination of ester groups and α-hydroxy thiol groups describedherein. Minimally, the hydroxy thiol ester comprises an average of atleast 1 α-hydroxy thiol group per hydroxy thiol ester molecule. In someembodiments, the hydroxy thiol ester composition comprises an average ofat least 1.5 α-hydroxy thiol groups per hydroxy thiol ester molecule;alternatively, an average of at least 2 α-hydroxy thiol groups perhydroxy thiol ester molecule; alternatively, an average of at least 2.5α-hydroxy thiol groups per hydroxy thiol ester molecule; oralternatively, an average of at least 3 α-hydroxy thiol groups perhydroxy thiol ester molecule. In other embodiments, the hydroxy thiolester composition comprises an average of from 1.5 to 9 α-hydroxy thiolgroups per hydroxy thiol ester molecule; alternatively, an average offrom 3 to 8 α-hydroxy thiol groups per hydroxy thiol ester molecule;alternatively, an average of from 2 to 4 α-hydroxy thiol groups perhydroxy thiol ester molecule; or alternatively, an average of from 4 to8 α-hydroxy thiol groups per hydroxy thiol ester molecule.

The hydroxy thiol esters can be produced by contacting an epoxidizedester derived from an unsaturated ester (i.e., epoxidized unsaturatedester), as described herein. In some instances it can desirable to haveepoxide groups present in the hydroxy thiol ester composition. While inother embodiments, it can be desirable to minimize the number of epoxygroups present in the hydroxy thiol ester composition. Thus, thepresence of residual epoxide groups can be another separate functionalgroup used to describe the hydroxy thiol ester.

The presence of epoxide groups in the hydroxy thiol ester can beindependently described as an average number of epoxide groups perhydroxy thiol ester, a molar ratio of epoxide groups to thiol groups, amolar ratio of epoxide groups to α-hydroxy thiol groups, or anycombination thereof. In some embodiments, the hydroxy thiol estermolecules comprise an average of less than 2 epoxide groups per hydroxythiol ester molecule, i.e., the hydroxy thiol ester molecules have amolar ratio of epoxide groups to α-hydroxy thiol groups of less than 2.Alternatively, the hydroxy thiol ester comprises an average of less than1.5 epoxide groups per hydroxy thiol ester molecule; alternatively, anaverage of less than 1 epoxide group per hydroxy thiol ester molecule;alternatively, an average of less than 0.75 epoxide groups per hydroxythiol ester molecule; or alternatively, an average of less than 0.5epoxide groups per hydroxy thiol ester molecule. In other embodiments,the molar ratio of epoxide groups to thiol groups averages less than1.5. Alternatively, the molar ratio of epoxide groups to thiol groupsaverages less than 1; alternatively, averages less than 0.75;alternatively, averages less than 0.5; alternatively, averages less than0.25; or alternatively, averages less than 0.1. In yet otherembodiments, the molar ratio of epoxide groups to α-hydroxy thiol groupsaverages less than 1.5. Alternatively, the molar ratio of epoxide groupsto α-hydroxy thiol groups averages less than 1; alternatively, averagesless than 0.75; alternatively, averages less than 0.5; alternatively,averages less than 0.25; or alternatively, averages less than 0.1.

In some embodiments, the hydroxy thiol ester composition issubstantially free of epoxide groups.

In other embodiments, the hydroxy thiol ester can be described by theaverage amount of thiol sulfur present in hydroxy thiol ester. In anembodiment, the hydroxy thiol ester molecules have an average of atleast 2.5 weight percent thiol sulfur per hydroxy thiol ester molecule;alternatively, an average of at least 5 weight percent thiol sulfur perhydroxy thiol ester molecule; alternatively, an average of at least 10weight percent thiol sulfur per hydroxy thiol ester molecule; oralternatively, an average of greater than 15 weight percent thiol sulfurper hydroxy thiol ester molecule. In an embodiment, the hydroxy thiolester molecules have an average of from 5 to 25 weight percent thiolsulfur per hydroxy thiol ester molecule; alternatively, an average offrom 5 to 20 weight percent thiol sulfur per hydroxy thiol estermolecule; alternatively, an average of from 6 to 15 weight percent thiolsulfur per hydroxy thiol ester molecule; or alternatively, an average offrom 8 to 10 weight percent thiol sulfur per hydroxy thiol estermolecule.

In some embodiments, at least 20 percent of the total side chainsinclude the α-hydroxy thiol group. In some embodiments, at least 20percent of the total side chains include the α-hydroxy thiol group. Insome embodiments, at least 60 percent of the total side chains includethe α-hydroxy thiol group; alternatively, at least 70 percent of thetotal side chains include the α-hydroxy thiol group. Yet in otherembodiments, at least 80 percent of the total side chains include theα-hydroxy thiol group.

In some aspects, greater than 20 percent of the hydroxy thiol estermolecule total side chains contain sulfur. In some aspects, greater than40 percent of the hydroxy thiol ester molecule total side chains containsulfur. In some aspects, greater than 60 percent of the hydroxy thiolester molecule total side chains contain sulfur; alternatively, greaterthan 70 percent of the total side chains contain sulfur; oralternatively, greater than 80 percent of the total side chains containsulfur.

In particular embodiments, the epoxidized unsaturated ester used in thesynthesis of the hydroxy thiol ester is produced from the epoxidizedunsaturated ester composition that includes an epoxidized natural sourceoil. Because the natural source oils have particular compositionsregarding the number of ester groups present, the hydroxy thiol esterwill have about the same number of ester groups as the feedstock naturalsource oil. Other independent properties that are described herein canbe used to further describe the hydroxy thiol ester.

In other embodiments, the epoxidized unsaturated ester used to producethe hydroxy thiol ester is produced from synthetic (or semi-synthetic)unsaturated ester oils. Because the synthetic ester oils can haveparticular compositions regarding the number of ester groups present,the hydroxy thiol ester would have about the same number of ester groupsas the synthetic ester oil. Other, independent properties of theunsaturated ester, whether the unsaturated ester includes natural sourceor synthetic oils, can be used to further describe the hydroxy thiolester composition.

The hydroxy thiol ester compositions can also be described as a productproduced by the process comprising contacting hydrogen sulfide and anepoxidized unsaturated ester composition and can be further limited bythe process as described herein. The hydroxy thiol containing naturalsource oil can also be described using an average molecular weight or anaverage molecular weight of the side chains.

Cross-Linked Thiol Ester Compositions

In an aspect, the present invention relates to a cross-linked thiolester composition. Generally, the cross-linked thiol ester molecules areoligomers of thiol esters that are connected together by polysulfidelinkages —S_(x)— wherein x is an integer greater 1. As the cross-linkedthiol ester is described as an oligomer of thiol esters, the thiolesters can be described as the monomer from which the cross-linked thiolesters are produced.

In an aspect, the cross-linked thiol ester composition comprises a thiolester oligomer having at least two thiol ester monomers connected by apolysulfide linkage having a structure —S_(Q)—, wherein Q is an integergreater than 1. In an aspect, the polysulfide linkage may be thepolysulfide linkage —S_(Q)—, wherein Q is 2, 3, 4, or mixtures thereof.In other embodiments, Q can be 2; alternatively, 3; or alternatively, 4.

In an aspect, the cross-linked thiol ester composition comprises a thiolester oligomer having at least 3 thiol ester monomers connected bypolysulfide linkages; alternatively, 5 thiol ester monomers connected bypolysulfide linkages; alternatively, 7 thiol ester monomers connected bypolysulfide linkages; or alternatively, 10 thiol ester monomersconnected by polysulfide linkages. In yet other embodiments, thecross-linked thiol ester composition comprises a thiol ester oligomerhaving from 3 to 20 thiol ester monomers connected by polysulfidelinkages; alternatively, from 5 to 15 thiol ester monomers connected bypolysulfide linkages; or alternatively, from 7 to 12 thiol estermonomers connected by polysulfide linkages.

In an aspect, the cross-linked thiol ester composition comprises thiolester monomers and thiol ester oligomers. In some embodiments, thecross-linked thiol ester composition has a combined thiol ester monomerand thiol ester oligomer average molecular weight greater than 2,000. Inother embodiments, the cross-linked thiol ester composition has acombined thiol ester monomer and thiol ester oligomer average molecularweight greater than 5,000; or alternatively, greater than 10,000. In yetother embodiments, the cross-linked thiol ester composition has acombined thiol ester monomer and thiol ester oligomer average molecularweight ranging from 2,000 to 20,000; alternatively, from 3,000 to15,000; or alternatively, from 7,500 to 12,500.

In an aspect, the thiol ester monomers and thiol ester oligomers have atotal thiol sulfur content greater than 0.5. In other embodiments, thethiol ester monomers and thiol ester oligomers have a total thiol sulfurcontent greater than 1; alternatively, greater than 2; alternatively,greater than 4. In yet other embodiments, the thiol ester monomers andthe thiol ester oligomers have a total thiol sulfur content from 0.5 to8; alternatively, from 4 to 8; or alternatively, 0.5 to 4.

In an aspect, the thiol ester monomers and thiol ester oligomers have atotal sulfur content greater than 8. In some embodiments, the thiolester monomers and thiol ester oligomers have a total sulfur contentgreater than 10; alternatively, greater than 12. In yet otherembodiments, the thiol ester monomers and thiol ester oligomers have atotal sulfur content ranging from 8 to 15 weight percent; alternatively,from 9 to 14; or alternatively, from 10 to 13.

The cross-linked thiol ester compositions can also be described as aproduct produced by the process comprising contacting a thiol ester withoxidizing agent and can be further limited by the process as describedherein.

Sulfide-Containing Ester Compositions

The present invention advantageously includes sulfide-containing estercompositions as embodiments of the present invention. Generally, thesulfide-containing ester compositions can be described as containingmolecules having at least one ester group and a least one sulfide groupwithin each molecule. The sulfide-containing esters used in the presentinvention can be produced by contacting either an unsaturated ester oran epoxidized unsaturated ester with a thiol containing compound asdescribed herein.

In addition to sulfide groups and ester groups, the sulfide-containingesters can further be described by including other functional groups andratios described herein. Each of the other functional groups, ratios,the number of sulfide groups, and the number of ester groups areseparate elements that allow the sulfide-containing ester to bedescribed using any combination of the sulfide-containing ester separateelements described herein. A non-limiting list of the sulfide-containingseparate elements include the average number of ester groups persulfide-containing ester molecule, the number of sulfide groups persulfide-containing ester molecule, the average number of moiety X persulfide-containing ester molecule, the average number of moiety Y persulfide-containing ester molecule, the average number of moiety Z persulfide-containing ester molecule, and the like.

The feedstock unsaturated esters can contain multiple carbon-carbondouble bonds per unsaturated ester molecule. The carbon-carbon doublebond reactivity and statistical probability, however, dictate that eachsulfide-containing ester molecule of the thiol-containing estercomposition produced from the unsaturated ester composition will nothave the same number of sulfide groups, number of unreactedcarbon-carbon double bonds, molar ratio of carbon-carbon double bonds tosulfide groups, molar ratio of cyclic sulfides to thiol groups and otherherein disclosed quantities of functional groups and molar ratios.Additionally, the feedstock unsaturated esters can also comprise amixture of individual unsaturated esters having a different number ofcarbon-carbon double bonds and/or ester groups. Many of these propertiesare discussed herein as an average number of the groups persulfide-containing ester molecule within the sulfide-containing estercomposition or average ratio per thiol-containing ester molecule withinthe sulfide-containing ester composition.

In embodiments related to the sulfide-containing ester that is producedfrom an epoxidized unsaturated ester, the feedstock epoxidizedunsaturated esters can contain multiple epoxide groups per unsaturatedester molecule. Individual epoxide group reactivity and statisticalprobability dictate that each sulfide-containing ester molecule of thesulfide-containing ester composition produced from the unsaturated estercomposition will not have the same number of sulfide groups, number ofunreacted epoxide groups, molar ratio of epoxide groups to sulfidegroups, and other herein disclosed quantities of functional groups andmolar ratios. Additionally, the feedstock epoxidized unsaturated esterscan also comprise a mixture of individual epoxidized unsaturated estermolecules having a different number of epoxide groups and/or estergroups. Thus, many of these properties are described as an averagenumber of the groups per sulfide-containing ester molecules within thesulfide-containing ester composition or average ratio perthiol-containing ester molecule within the sulfide-containing estercomposition.

Minimally, in some embodiments, the sulfide-containing esters compriseat least one ester group per sulfide-containing ester molecule. In someembodiments, the sulfide-containing ester has an average of at least 1.5ester groups per sulfide-containing ester molecule. Alternatively, thesulfide-containing ester molecules have an average of at least 2 estergroups per sulfide-containing ester molecule; alternatively, an averageof at least 2.5 ester groups per sulfide-containing ester molecule; oralternatively, an average of at least 3 ester groups persulfide-containing ester molecule. In other embodiments, thesulfide-containing esters have an average of from 1.5 to 9 ester groupsper sulfide-containing ester molecule; alternatively, an average of from1.5 to 8 ester groups per sulfide-containing ester molecule;alternatively, an average of from 2 to 8 ester groups persulfide-containing ester molecule; alternatively, an average of from 2to 7 ester groups per sulfide-containing ester molecule; alternatively,an average of from 2.5 to 5 ester groups per sulfide-containing estermolecule; alternatively, an average of from 3 to 5 ester groups persulfide-containing ester molecule; or alternatively, an average of from3 to 4 ester groups per sulfide-containing ester molecule. In yet otherembodiments, the hydroxy thiol-containing ester comprises an average ofabout 3 ester groups per sulfide-containing ester molecule; oralternatively, an average of about 4 ester groups per sulfide-containingester molecule.

Minimally, in some embodiments, the sulfide-containing ester moleculecomposition comprises sulfide-containing ester molecules having at leastone sulfide group per sulfide-containing ester molecule. In someembodiments, the sulfide-containing ester molecules have an average ofat least 1.5 sulfide groups per sulfide-containing ester molecule. Inother embodiments, the sulfide-containing ester molecules have anaverage of at least 2 sulfide groups per sulfide-containing estermolecule; alternatively, an average of at least 2.5 sulfide groups persulfide-containing ester molecule; or alternatively, an average of atleast 3 sulfide groups per sulfide-containing ester molecule. In otheraspects, the sulfide-containing ester molecules have an average of from1.5 to 9 sulfide groups per sulfide-containing ester molecule.Alternatively, the sulfide-containing ester molecules have an average offrom 3 to 8 sulfide groups per sulfide-containing ester molecule;alternatively, an average of from 2 to 4 sulfide groups persulfide-containing ester molecule; or alternatively, an average of from4 to 8 sulfide groups per sulfide-containing ester molecule.

In another independent aspect, the sulfide-containing ester compositioncomprising molecules having the moiety X:

In this moiety X structure, Q is hydrogen or a hydroxy group; R¹ and R²are independently selected from the group consisting of hydrogen, C₁ toC₂₀ organyl groups, and C₁ to C₂₀ hydrocarbyl groups; R³ is a C₁ to C₂₀organyl groups or a C₁ to C₂₀ hydrocarbyl groups; and the unspecifiedvalences of moiety X represent the remainder of the sulfide-containingester molecule. Q, R¹, R², and R³ are separate elements of moiety X thatallow moiety X to have any combination of further Q, R¹, R², and R³elements described herein. In some particular embodiments, R¹ and R² arehydrogen and R³ is a C₁ to C₂₀ organyl groups selected from the groupsdescribed herein.

In particular embodiments, the sulfide-containing ester molecules havean average of at least 1.5 moiety X's per sulfide-containing estermolecule. In other embodiments, the sulfide-containing ester moleculeshave an average of at least 2 moiety X's per sulfide-containing estermolecule; alternatively, an average of at least 2.5 moiety X's persulfide-containing ester molecule; or alternatively, an average of atleast 3 moiety X's per sulfide-containing ester molecule. In otheraspects, the sulfide-containing ester molecules have an average of from1.5 to 9 moiety X's per sulfide-containing ester molecule.Alternatively, the sulfide-containing ester molecules have an average offrom 3 to 8 moiety X's per sulfide-containing ester molecule;alternatively, an average of from 2 to 4 moiety X's persulfide-containing ester molecule; or alternatively, an average of from4 to 8 moiety X's per sulfide-containing ester molecule.

In a particular aspect, the sulfide-containing ester compositioncomprising molecules having the moiety Y:

In this moiety Y structure, R¹ and R² are independently selected fromthe group consisting of hydrogen and C₁ to C₂₀ hydrocarbyl groups; R³ isa C₁ to C₂₀ organyl groups or a C₁ to C₂₀ hydrocarbyl groups; and theunspecified valences of moiety Y represent the remainder of thesulfide-containing ester molecule. R¹, R², and R³ are separate elementsof moiety Y that allow moiety Y to have any combination of further R¹,R², and R³ embodiments as described herein. In some embodiments, R¹ andR² are hydrogen and R³ is a C₁ to C₂₀ organyl groups selected from thegroups described herein.

In particular embodiments, the sulfide-containing ester molecules havean average of at least 1.5 moiety Y's per sulfide-containing estermolecule. In other embodiments, the sulfide-containing ester moleculeshave an average of at least 2 moiety Y's per sulfide-containing estermolecule; alternatively, an average of at least 2.5 moiety Y's persulfide-containing ester molecule; or alternatively, an average of atleast 3 moiety Y's per sulfide-containing ester molecule. In otheraspects, the sulfide-containing ester molecules have an average of from1.5 to 9 moiety Y's per sulfide-containing ester molecule.Alternatively, the sulfide-containing ester molecules have an average offrom 3 to 8 moiety Y's per sulfide-containing ester molecule;alternatively, an average of from 2 to 4 moiety Y's persulfide-containing ester molecule; or alternatively, an average of from4 to 8 moiety Y's per sulfide-containing ester molecule.

In another particular aspect, the sulfide-containing ester compositioncomprising molecules having the moiety Z:

In this moiety Z structure, R¹ and R² are independently selected fromthe consisting of hydrogen and C₁ to C₂₀ hydrocarbyl groups; R³ is a C₁to C₂₀ organyl groups or a C₁ to C₂₀ hydrocarbyl groups; and theunspecified valences of moiety Z represent the remainder of thesulfide-containing ester molecule. R¹, R² and R³ are separate elementsof moiety Z that allow moiety Z to have any combination of further R¹,R², and R³ elements described herein. In some embodiments, R¹ and R² arehydrogen and R³ is a C₁ to C₂₀ organyl groups selected from the groupsdescribed herein.

In particular embodiments, the sulfide-containing ester molecules havean average of at least 1.5 moiety Z's per sulfide-containing estermolecule. In other embodiments, the sulfide-containing ester moleculeshave an average of at least 2 moiety Z's per sulfide-containing estermolecule; alternatively, an average of at least 2.5 moiety Z's persulfide-containing ester molecule; or alternatively, an average of atleast 3 moiety Z's per sulfide-containing ester molecule. In otheraspects, the sulfide-containing ester molecules have an average of from1.5 to 9 moiety Z's per sulfide-containing ester molecule.Alternatively, the sulfide-containing ester molecules have an average offrom 3 to 8 moiety Z's per sulfide-containing ester molecule;alternatively, an average of from 2 to 4 moiety Z's persulfide-containing ester molecule; or alternatively, an average of from4 to 8 moiety Z's per sulfide-containing ester molecule.

In some embodiments, R³ comprises at least one functional group. In oneaspect, the functional group is selected from the group consisting of ahydroxy group, a carboxylic acid group, a carboxylic ester group, anamine group, a sulfide group, and a second thiol group. In some aspects,R³ comprises at least two functional groups. In some aspects, thefunctional groups are selected from the group consisting of a hydroxygroup, carboxylic acid group, a carboxylic ester group, an amine group,a sulfide group, a second thiol group, and mixtures thereof.

As another embodiment of the present invention, a sulfide-containingester composition comprising sulfide-containing ester molecules isadvantageously provided. In this embodiment, the sulfide-containingester molecules have an average of least 1 ester group persulfide-containing ester molecule and have an average of at least 1moiety X per sulfide-containing ester molecule. The moiety X has thestructure as described herein. Additionally, the average number of estergroups and the average number of moiety X's are separate elements. Thus,the sulfide-containing ester molecules of the sulfide-containing estercomposition can have any combination of the average number of estergroups and the average number of moiety X's described herein.

As another embodiment of the present invention, a sulfide-containingester composition comprising sulfide-containing ester molecules isadvantageously provided. In this embodiment, the sulfide-containingester molecules have an average of least 1 ester group persulfide-containing ester molecule and have an average of at least 1moiety Y per sulfide-containing ester molecule. The moiety Y has thestructure as described herein. Additionally, the average number of estergroups and the average number of moiety Y's are separate elements. Thus,the sulfide-containing ester molecules of the sulfide-containing estercomposition can have any combination of the average number of estergroups and the average number of moiety Y's as described herein.

As another embodiment of the present invention, a sulfide-containingester composition comprising sulfide-containing ester molecules isadvantageously provided. In this embodiment, the sulfide-containingester molecules have an average of at least 1 ester group persulfide-containing ester molecule and have an average of at least 1moiety Z per sulfide-containing ester molecule. The moiety Z has thestructure as described herein. Additionally, the average number of estergroups and the average number of moiety Z's are separate elements. Thus,the sulfide-containing ester molecules of the sulfide-containing estercomposition can have any combination of the average number of estergroups and the average number of moiety Z's as described herein.

The sulfide-containing ester compositions can also be described as aproduct produced by the process comprising contacting an unsaturatedester with a mercaptan and can be further limited by the process asdescribed herein. In other embodiments, the sulfide-containing estercomposition can also be described as a product produced by a processcomprising contacting an epoxidized unsaturated ester with a mercaptanand can be further limited by the process as described herein.

Thioacrylate Ester Composition

As an embodiment of the present invention, a thioacrylate estercomposition is advantageously provided. Within the thioacrylate estercomposition descriptions, the terms “acrylate” and “thioacrylate” can beused to describe elements of the thioacrylate esters. Althoughthioacrylate groups could be considered as a member of the class ofacrylates, for the purposes of this thioacrylate ester compositiondescription contained herein, the term acrylate refers to the grouphaving the general structure:

The term thioacrylate refers to the group having the general structure:

Within this general thioacrylate structure, the unspecified valences onthe acrylate and thioacrylate carbon-carbon double bonds are furtherdefined herein.

Generally, the thioacrylate ester composition can be described ascomprising thioacrylate molecules having at least one ester group inaddition to any acrylate or thioacrylate ester groups present in thethioacrylate molecule and at least one thioacrylate group. The estergroup(s) that are in addition to any acrylate or thioacrylate estergroups present in the thioacrylate molecule are hereinafter referred toas “supplementary ester group(s).” The thioacrylate ester compositiondescribed herein can be produced by contacting an acrylate compositionwith a thiol-containing ester composition and/or a hydroxythiol-containing ester composition, both of which are described herein.

In addition to thioacrylate groups and supplementary ester groups, thethioacrylate ester composition can further be described by includingother functional groups and molar ratios described herein. Thethioacrylate groups, supplementary ester groups, the other functionalgroup, and molar ratios between functional groups present in thethioacrylate molecule represent separate elements of the thioacrylateester molecules that allow the thioacrylate ester composition to bedescribed using any combination of the thioacrylate ester separateelements described herein. A non-limiting list of the thioacrylate esterindependent elements include: the number of supplementary ester groups,the average number of supplementary ester groups per thioacrylate estermolecule, the number of thioacrylate groups, the number of thioacrylategroups per thioacrylate ester molecule, the number of acrylate groups,the average number of acrylate groups per thioacrylate ester molecule,the number of moiety X¹'s, the average number of moiety X¹'s perthioacrylate ester molecule, the number of moiety Y¹'s, the averagenumber of moiety Y¹'s per thioacrylate ester molecule, the number ofmoiety Z¹'s, the average number of moiety Z¹'s per thioacrylate estermolecule, and the like.

The feedstock thiol ester compositions and/or hydroxy thiol estercompositions can comprise a mixture of molecules that have an averagequantity of ester groups, thiol groups, hydroxy groups, and other groupsand molar ratios described herein. Additionally, individual thiol andhydroxy group reactivity within the thiol-containing ester compositionsand/or hydroxy thiol ester compositions and statistical probabilitydictate that each thioacrylate ester molecule of the thioacrylate estercomposition produced may not have the same number of ester groups,thioacrylate groups, acrylate groups, and other herein disclosedquantities of functional groups, moieties, and molar ratios. Thus, manyof the properties of the thioacrylate ester molecules within thethioacrylate ester composition are described as using an average numberof the groups per thioacrylate ester molecule within the thioacrylateester composition or as an average ratio per thioacrylate ester moleculewithin the thioacrylate ester composition.

Minimally, in some embodiments, the thioacrylate ester compositioncomprises at least 1 supplementary ester group per thioacrylate estermolecule. In some embodiments, the thioacrylate ester has an average ofat least 1.5 supplementary ester groups per thioacrylate ester molecule.Alternatively, the thioacrylate ester molecules have an average of atleast 2 supplementary ester groups per thioacrylate ester molecule;alternatively, an average of at least 2.5 supplementary ester groups perthioacrylate ester molecule; or alternatively, an average of at least 3supplementary ester groups per thioacrylate ester molecule. In otherembodiments, the thioacrylate ester has an average of from 1.5 to 9supplementary ester groups per thioacrylate ester molecule;alternatively, an average of from 1.5 to 8 supplementary ester groupsper thioacrylate ester molecule; alternatively, an average of from 2 to8 supplementary ester groups per thioacrylate ester molecule;alternatively, an average of from 2 to 7 supplementary ester groups perthioacrylate ester molecule; alternatively, an average of from 2.5 to 5supplementary ester groups per thioacrylate ester molecule;alternatively, an average of from 3 to 5 supplementary ester groups perthioacrylate ester molecule; or alternatively, an average of from 3 to 4supplementary ester groups per thioacrylate ester molecule. In yet otherembodiments, the thioacrylate ester comprises an average of about 3supplementary ester groups per thioacrylate ester molecule; oralternatively, an average of about 4 supplementary ester groups perthioacrylate ester molecule.

Minimally, in some embodiments, the thioacrylate ester comprises atleast 1 thioacrylate group. In some embodiments of the presentinvention, the thioacrylate ester molecules have an average of at least1.5 thioacrylate groups per thioacrylate ester molecule. In otherembodiments, the thioacrylate ester molecules have an average of atleast 2 thioacrylate groups per thioacrylate ester molecule;alternatively, an average of at least 2.5 thioacrylate groups perthioacrylate ester molecule; or alternatively, an average of at least 3thioacrylate groups per thioacrylate ester molecule. In an aspect, thethioacrylate ester molecules have an average of from 1.5 to 9thioacrylate groups per thioacrylate ester molecule; alternatively, anaverage of from 3 to 8 thioacrylate groups per thioacrylate estermolecule; alternatively, an average of from 2 to 4 thioacrylate groupsper thioacrylate ester molecule; or alternatively, an average of from 4to 8 thioacrylate groups per thioacrylate ester molecule.

In some aspects of the present invention, the thioacrylate estermolecules further comprise acrylate groups. In some embodiments, thethioacrylate ester molecules have an average of at least 1 acrylategroup per thioacrylate ester molecule. In other embodiments, thethioacrylate ester molecules have an average of at least 1.5 acrylategroups per thioacrylate ester molecule; alternatively, an average of atleast 2 acrylate groups per thioacrylate ester molecule; alternatively,an average of at least 2.5 acrylate groups per thioacrylate estermolecule; or alternatively, an average of at least 3 acrylate groups perthioacrylate ester molecule. In an aspect, the thioacrylate estermolecules have an average of from 1.5 to 9 acrylate groups perthioacrylate ester molecule; alternatively, an average of from 3 to 8acrylate groups per thioacrylate ester molecule; alternatively, anaverage of from 2 to 4 acrylate groups per thioacrylate ester molecule;or alternatively, an average of from 4 to 8 acrylate groups perthioacrylate ester molecule.

As another embodiment of the present invention, a thioacrylatecomposition comprising thioacrylate ester molecules have an average ofat least 1 supplementary ester group per thioacrylate ester molecule andan average of at least 1 moiety X¹ per thioacrylate ester molecule, themoiety X¹ having the structure:

In the moiety X¹ structure, R^(t1) and R^(t2) are independently selectedfrom the group consisting of consisting of hydrogen, C₁ to C₂₀ organylgroups, and C₁ to C₂₀ hydrocarbyl groups; Q^(t1) is independentlyselected from the group consisting of hydrogen and an acrylate group;and TA represents a thioacrylate group having the structure:

The unspecified valences of moiety X¹ represent the remainder of thethioacrylate ester molecule. Within the embodiments wherein thethioacrylate ester molecules contain the moiety X¹, the average numberof supplementary ester groups per thioacrylate ester and the averagenumber of moiety X¹ present in the thioacrylate molecules perthioacrylate ester molecule are separate elements.

In further embodiments, the thioacrylate ester molecules have an averageof at least 1.5 moiety X¹'s per thioacrylate ester molecule. In otherembodiments, the thioacrylate ester molecules have an average of atleast 2 moiety X¹'s per thioacrylate ester molecule; alternatively, anaverage of at least 2.5 moiety X¹'s per thioacrylate ester molecule; oralternatively, an average of at least 3 moiety X¹'s per thioacrylateester molecule. In an aspect, the thioacrylate ester molecules have anaverage of from 1.5 to 9 moiety X¹'s per thioacrylate ester molecule;alternatively, an average of from 3 to 8 moiety X¹'s per thioacrylateester molecule; alternatively, an average of from 2 to 4 moiety X¹'s perthioacrylate ester molecule; or alternatively, an average of from 4 to 8moiety X¹'s per thioacrylate ester molecule.

In some embodiments the thioacrylate ester has a thioacrylate grouphaving the structure:

Generally, within the thioacrylate group structure, R⁴, R⁵, and R⁶ areindependently selected from the group consisting of hydrogen, C₁ to C₂₀organyl groups, and C₁ to C₂₀ hydrocarbyl groups. In furtherembodiments, R⁴, R⁵, and R⁶ are selected from hydrogen, C₁ to C₁₀organyl groups, and C₁ to C₁₀ hydrocarbyl groups; or alternatively,selected from C₁ to C₅ organyl groups, and C₁ to C₅ hydrocarbyl groups.In certain embodiments, R⁴, R⁵, and R⁶ are independently selected fromthe group consisting of hydrogen and a methyl group. In some specificembodiments, R⁵ and R⁶ are hydrogen and R⁴ is selected from hydrogen, amethyl group, or a mixture thereof; alternatively, R and R⁶ are hydrogenand R⁴ is a methyl group; or alternatively, R⁴, R⁵, and R⁶ are hydrogen.

In some embodiments the thioacrylate ester has an acrylate group havingthe structure:

Generally, within the acrylate group structure, R⁷, R⁸, and R⁹ areindependently selected from the group consisting of hydrogen, C₁ to C₂₀organyl groups, and C₁ to C₂₀ hydrocarbyl groups. In furtherembodiments, R⁷, R⁸, and R⁹ are selected from hydrogen, C₁ to C₁₀organyl groups, and C₁ to C₁₀ hydrocarbyl groups; or alternatively,selected from C₁ to C₅ organyl groups and C₁ to C₅ hydrocarbyl groups.In certain embodiments, R⁷, R⁸, and R⁹ are independently selected fromthe group consisting of hydrogen and a methyl group. In some specificembodiments, R⁸ and R⁹ are hydrogen and R⁷ is selected from hydrogen, amethyl group, or a mixture thereof; alternatively, R⁸ and R⁹ arehydrogen and R⁷ is a methyl group; or alternatively, R⁷, R⁸, and R⁹ arehydrogen.

As another embodiment of the present invention, a thioacrylatecomposition comprising thioacrylate ester molecules is advantageouslyprovided. In this embodiment, the thioacrylate ester molecules have anaverage of at least 1 supplementary ester group per thioacrylate estermolecule and an average of at least 1 moiety Y¹ per thioacrylate estermolecule, the moiety Y¹ having the structure:

In the moiety Y¹ structure, R^(t1) and R^(t2) are independently selectedfrom the group consisting of hydrogen, C₁ to C₂₀ organyl groups, and C₁to C₂₀ hydrocarbyl groups, and TA represents a thioacrylate group havingthe structure:

The unspecified valences of moiety Y¹ represent the remainder of thethioacrylate ester molecule. Within the embodiments related to thethioacrylate ester molecules containing the moiety Y¹, the averagenumber of supplementary ester groups per thioacrylate ester and theaverage number of moiety Y¹ present in the thioacrylate molecules perthioacrylate ester molecule are separate elements.

In further embodiments, the thioacrylate ester molecules have an averageof at least 1.5 moiety Y¹'s per thioacrylate ester molecule. In otherembodiments, the thioacrylate ester molecules have an average of atleast 2 moiety Y¹'s per thioacrylate ester molecule; alternatively, anaverage of at least 2.5 moiety Y¹'s per thioacrylate ester molecule; oralternatively, an average of at least 3 moiety Y¹'s per thioacrylateester molecule. In an aspect, the thioacrylate ester molecules have anaverage of from 1.5 to 9 moiety Y¹'s per thioacrylate ester molecule;alternatively, an average of from 3 to 8 moiety Y¹'s per thioacrylateester molecule; alternatively, an average of from 2 to 4 moiety Y¹'s perthioacrylate ester molecule; or alternatively, an average of from 4 to 8moiety Y¹'s per thioacrylate ester molecule.

As another embodiment of the present invention, a thioacrylatecomposition comprising thioacrylate ester molecules is advantageouslyprovided. In this embodiment, the thioacrylate ester molecules have anaverage of at least 1 supplementary ester group per thioacrylate estermolecule and an average of at least 1 moiety Z¹ per thioacrylate estermolecule, the moiety Z¹ having the structure:

In the moiety Z¹ structure, R^(t1) and R^(t2) are independently selectedfrom the group consisting of consisting of hydrogen, C₁ to C₂₀ organylgroups, and C₁ to C₂₀ hydrocarbyl groups; Q^(t1) is independentlyselected from the group consisting of hydrogen and an acrylate group; TArepresents a thioacrylate group having the structure:

and A represents a acrylate group having the structure:

The unspecified valences of moiety Z¹ represent the remainder of thethioacrylate ester molecule. Within the embodiments where thethioacrylate ester molecules contain the moiety Z¹, the average numberof supplementary ester groups per thioacrylate ester and the averagenumber of moiety Z¹'s present in the thioacrylate molecules perthioacrylate ester molecule are independent elements.

In further embodiments, the thioacrylate ester molecules have an averageof at least 1.5 moiety Z¹'s per thioacrylate ester molecule. In otherembodiments, the thioacrylate ester molecules have an average of atleast 2 moiety Z¹'s per thioacrylate ester molecule; alternatively, anaverage of at least 2.5 moiety Z¹'s per thioacrylate ester molecule; oralternatively, an average of at least 3 moiety Z¹'s per thioacrylateester molecule. In an aspect, the thioacrylate ester molecules have anaverage of from 1.5 to 9 moiety Z¹'s per thioacrylate ester molecule;alternatively, an average of from 3 to 8 moiety Z¹'s per thioacrylateester molecule; alternatively, an average of from 2 to 4 moiety Z¹'s perthioacrylate ester molecule; or alternatively, an average of from 4 to 8moiety Z¹'s per thioacrylate ester molecule.

As another embodiment of the present invention, a thioacrylate estercomposition comprising thioacrylate ester molecules is advantageouslyprovided. In this embodiment, the thioacrylate ester molecules have anaverage of least 1 supplementary ester group per thioacrylate estermolecule and have an average of at least 1 moiety X¹ per thioacrylateester molecule. The moiety X¹ has the structure as described herein.Additionally, the average number of supplementary ester groups perthioacrylate ester molecule and the average number of moiety X¹'s areindependent elements.

As another embodiment of the present invention, a thioacrylate estercomposition comprising thioacrylate ester molecules is advantageouslyprovided. In this embodiment, the thioacrylate ester molecules have anaverage of least 1 supplementary ester group per thioacrylate estermolecule and have an average of at least 1 moiety Y¹ per thioacrylateester molecule. The moiety Y¹ has the structure described herein.Additionally, the average number of supplementary ester groups perthioacrylate ester molecule and the average number of moiety Y¹'s areindependent elements.

As another embodiment of the present invention, a thioacrylate estercomposition comprising thioacrylate ester molecules is advantageouslyprovided. In this embodiment, the thioacrylate ester molecules have anaverage of least 1 supplementary ester group per thioacrylate estermolecule and have an average of at least 1 moiety Z¹ per thioacrylateester molecule. The moiety Z¹ has the structure described herein.Additionally, the average number of supplementary ester groups perthioacrylate ester molecule and the average number of moiety Z¹'s areindependent elements.

In some embodiments, there is provided a thioacrylate moleculecomprising one supplementary ester group and a thioacrylate group havingthe structure:

In this thioacrylate group structure, R⁴, R⁵, and R⁶ are independentlyselected from the group consisting of hydrogen, C₁ to C₂₀ organylgroups, and C₁ to C₂₀ hydrocarbyl groups. The supplementary ester groupand the thioacrylate group of the thioacrylate molecule representindependent elements. The thioacrylate molecule can have any combinationof these elements described herein. Additionally, each R⁴, R⁵, and R⁶group of the thioacrylate structure represents an independent element.The thioacrylate structure described herein can have any combination ofthe R⁴, R⁵, and R⁶ groups.

In some embodiments, the thioacrylate ester molecule comprisingsupplementary ester groups and a thioacrylate group has at least 1supplementary ester group. In other embodiments the thioacrylatemolecule has at least 2 supplementary ester groups; or alternatively, atleast 3 supplementary ester groups. In other embodiments, thethioacrylate ester molecule that includes supplementary ester groups anda thioacrylate group has from 2 to 9 supplementary ester groups;alternatively, from 2 to 8 supplementary ester groups; alternatively,from 2 to 7 supplementary ester groups; alternatively, from 3 to 5supplementary ester groups; or alternatively, from 3 to 4 supplementaryester groups. In yet other embodiments, the thioacrylate ester includes3 supplementary ester groups or alternatively, includes 4 supplementaryester groups.

In further embodiments, the thioacrylate ester molecule that includessupplementary ester groups and a thioacrylate group can further includeat least 1 thioacrylate groups; alternatively, at least 2 thioacrylategroups; or alternatively, at least three thioacrylate groups. In otherembodiments, the thioacrylate ester molecule comprises from 2 to 9thioacrylate groups; alternatively, from 3 to 8 thioacrylate groups;alternatively, from 2 to 4 thioacrylate groups; or alternatively, from 4to 8 thioacrylate groups.

In other embodiments, the thioacrylate ester molecule that includessupplementary ester groups and a thioacrylate group can further includeacrylate groups having the structure:

In this acrylate group structure, R⁷, R⁸, and R⁹ are independentlyselected from the group consisting of hydrogen, C₁ to C₂₀ organylgroups, and C₁ to C₂₀ hydrocarbyl groups. In some embodiments thethioacrylate ester molecule comprises at least 2 acrylate groups; oralternatively, at least three acrylate groups. In other embodiments, thethioacrylate ester molecule comprises from 2 to 9 acrylate groups;alternatively, from 3 to 8 acrylate groups; alternatively, from 2 to 4acrylate groups; or alternatively, from 4 to 8 acrylate groups.

In some embodiments, the thioacrylate ester molecule includes at leastone supplementary ester group and a least one moiety Y¹ having thestructure:

In this moiety Y¹ structure, R^(t1) and R^(t2) are independentlyselected from the group consisting of consisting of hydrogen, C₁ to C₂₀organyl groups, and C₁ to C₂₀ hydrocarbyl groups, and TA represents athioacrylate group having the structure:

The unspecified valences of moiety Y¹ represent the remainder of thethioacrylate ester molecule. The supplementary ester groups and themoiety Y¹ of the thioacrylate molecule represent independent elements.The thioacrylate molecule can have any combination of these elementsdescribed herein. Other embodiments of the number of supplementary estergroups have been described herein. Additional embodiments of the R⁴, R⁵,and R⁶ groups containing the thioacrylate structure are describedherein.

The thioacrylate ester molecule that includes supplementary ester groupsand moiety Y¹ can include any combination of the number of supplementaryester groups and any number of moiety Y¹'s described herein. The numberof ester groups within the thioacrylate ester molecule that includessupplementary ester groups and moiety Y¹ are described herein. Infurther embodiments, the thioacrylate ester molecule that includessupplementary ester groups and moiety Y¹ can include at least 1 moietyY¹; alternatively, at least 2 moiety Y¹'s; or alternatively, at least 3moiety Y¹'s. In other embodiments, the thioacrylate ester molecule thatincludes supplementary ester groups and moiety Y¹ includes from 2 to 9moiety Y¹'s; alternatively, from 3 to 8 moiety Y¹'s; alternatively, from2 to 4 moiety Y¹'s; or alternatively, from 4 to 8 moiety Y¹'s.

The thioacrylate ester can also be described as a product produced bythe process that includes contacting a thiol-containing estercomposition with an acrylate composition and can be further limited bythe process described herein. In other embodiments, the thioacrylateester composition can also be described as a product produced by aprocess that includes contacting a hydroxy thiol-containing estercomposition with an acrylate composition and can be further limited bythe process described herein.

Sulfonic Acid-Containing Esters

The present invention advantageously provides a sulfonic acid-containingester as an embodiment of the present invention. Generally, the sulfonicacid-containing ester of the present invention includes sulfonicacid-containing ester molecules having at least one ester group and aleast one sulfonic acid group. The sulfonic acid-containing esterdescribed herein can be produced by contacting a thiol ester with anoxidizing agent as described herein. Because the feedstock for theproduction of the sulfonic acid-containing ester can include multiplethiols groups, thiol group reactivity and statistical probabilitydictate that each sulfonic acid-containing ester molecule of thesulfonic acid-containing ester will not have the same number of sulfonicacid groups. Additionally, the feedstock thiol ester can also include amixture of individual thiol ester molecules having different numbers ofthiol groups and/or ester groups. Thus, many of the groups present inthe sulfonic acid-containing ester are described herein as an averagenumber of the groups per sulfonic acid-containing ester molecule or anaverage ratio per sulfonic acid-containing ester molecule within thesulfonic acid-containing ester.

The number of sulfonic acid groups and the number of ester groupscontained within the sulfonic acid-containing ester are separateelements that allow the sulfonic acid-containing ester to be describedusing any combination of the sulfonic acid-containing ester separateelements described herein. A non-limiting list of the sulfonicacid-containing ester separate elements include the number of estergroups, the average number of ester groups per sulfonic acid-containingester molecule, the number of sulfonic acid groups, the average numberof sulfonic acid groups per sulfonic acid-containing ester molecule, thenumber of moiety X²'s, the average number of moiety X²'s per sulfonicacid-containing ester molecule, ester molecule, the number of moietyY²'s, the average number of Y² per sulfonic acid-containing estermolecule, ester molecule, the number of moiety Z²'s, the average numberof moiety Z²'s per sulfonic acid-containing ester molecule, and thelike.

Minimally, the sulfonic acid-containing ester includes at least oneester group per sulfonic acid-containing ester molecule. In someembodiments, the sulfonic acid-containing ester has an average of atleast 1.5 ester groups per sulfonic acid-containing ester molecule.Alternatively, the sulfonic acid-containing ester has an average of atleast 2 ester groups per sulfonic acid-containing ester molecule;alternatively, an average of at least 2.5 ester groups per sulfonicacid-containing ester molecule; or alternatively, an average of at least3 ester groups per sulfonic acid-containing ester molecule. In otherembodiments, the sulfonic acid-containing ester has an average of from1.5 to 9 ester groups per sulfonic acid-containing ester molecule;alternatively, an average of from 1.5 to 8 ester groups per sulfonicacid-containing ester molecule; alternatively, an average of from 2 to 8ester groups per sulfonic acid-containing ester molecule; alternatively,an average of from 2 to 7 ester groups per sulfonic acid-containingester molecule; alternatively, an average of from 2.5 to 5 ester groupsper sulfonic acid-containing ester molecule; alternatively, an averageof from 3 to 5 ester groups per sulfonic acid-containing ester molecule;or alternatively, an average of from 3 to 4 ester groups per sulfonicacid-containing ester molecule. In yet other embodiments, the sulfonicacid-containing ester comprises an average of 3 ester groups persulfonic acid-containing ester molecule or alternatively, an average of4 ester groups per sulfonic acid-containing ester molecule.

Minimally, the sulfonic acid-containing ester molecules have an averageof at least one sulfonic acid group per sulfonic acid-containing estermolecule. In some embodiments, the sulfonic acid ester has an average ofat least 1.5 sulfonic acid groups per sulfonic acid-containing estermolecule; alternatively, have an average of at least 2 sulfonic acidgroups per sulfonic acid-containing ester molecule; alternatively, anaverage of at least 2.5 sulfonic acid groups per sulfonicacid-containing ester molecule; or alternatively, an average of at least3 sulfonic acid groups per sulfonic acid-containing ester molecule. Inother embodiments, the sulfonic acid-containing ester has an average offrom 1.5 to 9 sulfonic acid groups per sulfonic acid-containing estermolecule; alternatively, an average of from 3 to 8 sulfonic acid groupsper sulfonic acid-containing ester molecule; alternatively, an averageof from 2 to 4 sulfonic acid groups per sulfonic acid-containing estermolecule; or alternatively, an average of from 4 to 8 sulfonic acidgroups per sulfonic acid-containing ester molecule.

In another aspect, the sulfonic acid-containing ester further includes ahydroxy group. In some embodiments, the sulfonic acid-containing estercomprises an average of at least 1 hydroxy group per sulfonicacid-containing ester molecule.

In some embodiments of the present invention, the sulfonic acid ester issubstantially free of thiol groups.

In another independent aspect, the sulfonic acid-containing esterincludes an average of at least one ester group per sulfonicacid-containing ester molecule and an average of at least one moiety X²per sulfonic acid-containing ester molecule wherein the moiety X² hasthe structure:

In this moiety X² structure, Q^(s1) is hydrogen or a hydroxy group;R^(s1) and R^(s2) are independently selected from the group consistingof hydrogen, C₁ to C₂₀ organyl groups, and C₁ to C₂₀ hydrocarbyl groups;and the unspecified valences of moiety X² represent the remainder of thesulfonic acid-containing ester molecule. Q^(s1), R^(s1), and R^(s2) areseparate elements of moiety X² that allow moiety X² to have anycombination of further Q^(s1), R^(s1), and R^(s2) elements describedherein. In some particular embodiments, R^(s1) and R^(s2) are hydrogen.

In particular embodiments, the sulfonic acid-containing ester has anaverage of at least 1.5 moiety X²'s per sulfonic acid-containing estermolecule. In other embodiments, the sulfonic acid-containing ester hasan average of at least 2 moiety X²'s per sulfonic acid ester molecule;alternatively, an average of at least 2.5 moiety X²'s per sulfonicacid-containing ester molecule; or alternatively, an average of at least3 moiety X²'s per sulfonic acid-containing ester molecule. In otheraspects, the sulfonic acid-containing ester has an average of from 1.5to 9 moiety X²'s per sulfonic acid-containing ester molecule.Alternatively, the sulfonic acid-containing ester have an average offrom 3 to 8 moiety X²'s per sulfonic acid-containing ester molecule;alternatively, an average of from 2 to 4 moiety X²'s per sulfonicacid-containing ester molecule; or alternatively, an average of from 4to 8 moiety X²'s per sulfonic acid-containing ester molecule.

In another independent aspect, the sulfonic acid-containing esterincludes an average of at least one ester group per sulfonicacid-containing ester molecule and an average of at least one moiety Y²per sulfonic acid-containing ester molecule wherein the moiety Y² hasthe structure:

In this moiety Y² structure, R^(s1) and R^(s2) are independentlyselected from the group consisting of hydrogen, C₁ to C₂₀ organylgroups, and C, to C₂₀ hydrocarbyl groups, and the unspecified valencesof moiety Y² represent the remainder of the sulfonic acid-containingester molecule. R^(s1) and R^(s2) are separate elements of moiety Y²that allow moiety Y² to have any combination of further R^(s1), andR^(s2) elements described herein. In some particular embodiments, R^(s1)and R^(s2) are hydrogen.

In particular embodiments, the sulfonic acid-containing ester has anaverage of at least 1.5 moiety Y²'s per sulfonic acid-containing estermolecule. In other embodiments, the sulfonic acid-containing ester hasan average of at least 2 moiety Y²'s per sulfonic acid ester molecule;alternatively, an average of at least 2.5 moiety Y²'s per sulfonicacid-containing ester molecule; or alternatively, an average of at least3 moiety Y²'s per sulfonic acid-containing ester molecule. In otheraspects, the sulfonic acid-containing ester has an average of from 1.5to 9 moiety Y²'s per sulfonic acid-containing ester molecule.Alternatively, the sulfonic acid-containing ester has an average of from3 to 8 moiety Y²'s per sulfonic acid-containing ester molecule;alternatively, an average of from 2 to 4 moiety Y²'s per sulfonicacid-containing ester molecule; or alternatively, an average of from 4to 8 moiety Y²'s per sulfonic acid-containing ester molecule.

In another independent aspect, the sulfonic acid-containing esterincludes an average of at least one ester group per sulfonicacid-containing ester molecule and an average of at least one moiety Z²per sulfonic acid-containing ester molecule wherein the moiety Z² hasthe structure:

In the moiety Z² structure, R^(s1) and R^(s2) are independently selectedfrom the group consisting of hydrogen, C₁ to C₂₀ organyl groups, and C₁to C₂₀ hydrocarbyl groups, and the unspecified valences of moiety Y²represent the remainder of the sulfonic acid-containing ester molecule.R^(s1), and R^(s2) are separate elements of moiety Z² that allow moietyZ² to have any combination of further R^(s1), and R^(s2) elementsdescribed herein. In some particular embodiments, R^(s1) and R^(s2) arehydrogen.

In particular embodiments, the sulfonic acid-containing ester has anaverage of at least 1.5 moiety Z²'s per sulfonic acid-containing estermolecule. In other embodiments, the sulfonic acid-containing ester hasan average of at least 2 moiety Z²'s per sulfonic acid ester molecule;alternatively, an average of at least 2.5 moiety Z²'s per sulfonicacid-containing ester molecule; or alternatively, an average of at least3 moiety Z²'s per sulfonic acid-containing ester molecule. In otheraspects, the sulfonic acid-containing ester has an average of from 1.5to 9 moiety Z²'s per sulfonic acid-containing ester molecule.Alternatively, the sulfonic acid-containing ester has an average of from3 to 8 moiety Z²'s per sulfonic acid-containing ester molecule;alternatively, an average of from 2 to 4 moiety Z²'s per sulfonicacid-containing ester molecule; or alternatively, an average of from 4to 8 moiety Z²'s per sulfonic acid-containing ester molecule.

As another embodiment of the present invention, a sulfonicacid-containing ester comprising sulfonic acid-containing estermolecules is advantageously provided. In this embodiment, the sulfonicacid-containing ester molecules have an average of least 1 ester groupper sulfonic acid-containing ester molecule and have an average of atleast 1 moiety X² per sulfonic acid-containing ester molecule. Themoiety X² has the structure described herein. Additionally, the averagenumber of ester groups and the average number of moiety X²'s areseparate elements that allow the sulfonic acid-containing estermolecules of the sulfonic acid-containing ester to have any combinationof the average number of ester groups and the average number of moietyX²'s described herein.

As another embodiment of the present invention, a sulfonicacid-containing ester comprising sulfonic acid-containing estermolecules is advantageously provided. In this embodiment, the sulfonicacid-containing ester has an average of least 1 ester group per sulfonicacid-containing ester molecule and have an average of at least 1 moietyY² per sulfonic acid-containing ester molecule. The moiety Y² has thestructure described herein. Additionally, the average number of estergroups and the average number of moiety Y²'s are separate elements thatallow the sulfonic acid-containing ester molecules of the sulfonicacid-containing ester composition to have any combination of the averagenumber of ester groups and the average number of moiety Y²'s describedherein.

As another embodiment of the present invention, a sulfonicacid-containing ester comprising sulfonic acid-containing estermolecules is advantageously provided. In this embodiment, the sulfonicacid-containing ester has an average of least 1 ester group per sulfonicacid-containing ester molecule and have an average of at least 1 moietyZ² per sulfonic acid-containing ester molecule. The moiety Z² has thestructure described herein. Additionally, the average number of estergroups and the average number of moiety Z²'s are separate elements thatallow the sulfonic acid-containing ester molecules of the sulfonicacid-containing ester to have any combination of the average number ofester groups and the average number of moiety Z²'s described herein.

In some embodiments, there is provided a sulfonic acid-containing estermolecule comprising at least one ester group and at least one sulfonicacid group. The number of ester groups and the number of sulfonic acidgroups are separate elements that allow the sulfonic acid-containingester molecule to contain any number of ester groups and sulfonic acidgroups described herein.

In some embodiments, the sulfonic acid-containing ester moleculecomprises at least 2 ester groups. Alternatively, in some embodiments,the sulfonic acid-containing ester molecule comprises at least 3 estergroups. In one aspect, the sulfonic acid-containing ester moleculecomprises from 2 to 9 ester groups per sulfonic acid-containing estermolecule. In one aspect, the sulfonic acid-containing ester moleculecomprises from 2 to 8 ester groups per sulfonic acid-containing estermolecule; alternatively, from 2 to 7 ester groups; alternatively, from 3to 5 ester groups per sulfonic acid-containing ester molecule; oralternatively, from 3 to 4 ester groups. In yet other embodiments, thesulfonic acid-containing ester molecule comprises 3 ester groups; oralternatively, comprises 4 ester groups.

In further embodiments, the sulfonic acid-containing ester moleculecomprises at least one ester group and at least one sulfonic acid. Inother embodiments, the sulfonic acid-containing ester molecule comprisesat least 2 sulfonic acid groups; or alternatively, at least threesulfonic acid groups. In other embodiments, the sulfonic acid-containingester molecule comprises from 2 to 9 sulfonic acid groups;alternatively, from 3 to 8 sulfonic acid groups; alternatively, from 2to 4 sulfonic acid groups; or alternatively, from 4 to 8 sulfonic acidgroups.

In some embodiments, the sulfonic acid-containing ester moleculecomprises at least one ester group and a least one moiety X². Thesulfonic acid-containing ester molecule comprising ester groups andmoiety X² may comprise any combination of the number of ester groups andany number of moiety X²'s as described herein. The number of estergroups within the sulfonic acid-containing ester molecule comprisingester groups and moiety X² has been described previously. In furtherembodiments, the sulfonic acid-containing ester molecule comprisingester groups and moiety X² can comprise at least 1 moiety X²;alternatively, at least 2 moiety X²'s; or alternatively, at least 3moiety X²'s. In other embodiments, the sulfonic acid-containing estermolecule that includes ester groups and moiety X² comprises from 2 to 9moiety X²'s; alternatively, from 3 to 8 moiety X²'s; alternatively, from2 to 4 moiety X²'s; or alternatively, from 4 to 8 moiety X²'s.

In some embodiments, the sulfonic-containing acid ester moleculecomprises at least one ester group and a least one moiety Y². Thesulfonic acid-containing ester molecule comprising ester groups andmoiety Y² can include any combination of the number of ester groups andany number of moiety Y²'s described herein. The number of ester groupswithin the sulfonic acid-containing ester molecule comprising estergroups and moiety Y² has been described previously. In furtherembodiments, the sulfonic acid-containing ester molecule comprisingester groups and moiety Y² can include at least 1 moiety Y²;alternatively, at least 2 moiety Y²'s; or alternatively, at least 3moiety Y²'s. In other embodiments, the sulfonic acid-containing estermolecule comprising ester groups and moiety Y² includes from 2 to 9moiety Y²'s; alternatively, from 3 to 8 moiety Y²'s; alternatively, from2 to 4 moiety Y²'s; or alternatively, from 4 to 8 moiety Y²'s.

In some embodiments, the sulfonic acid-containing ester moleculecomprises at least one ester group and a least one moiety Z². Thesulfonic acid-containing ester molecule comprising ester groups andmoiety Z² may comprise any combination of the number of ester groups andany number of moiety Z²'s as described herein. The number of estergroups within the sulfonic acid-containing ester molecule comprisingester groups and moiety Z² has been described previously. In furtherembodiments, the sulfonic acid-containing ester molecule comprisingester groups and moiety Z² can include at least 1 moiety Z²;alternatively, at least 2 moiety Z²'s; or alternatively, at least 3moiety Z²'s. In other embodiments, the sulfonic acid-containing estermolecule comprising ester groups and moiety Z² includes from 2 to 9moiety Z²'s; alternatively, from 3 to 8 moiety Z²'s; alternatively, from2 to 4 moiety Z²'s; or alternatively, from 4 to 8 moiety Z²'s.

The sulfonic acid-containing ester can also be described as a productproduced by the process comprising contacting a thiol ester with anoxidizing agent described herein.

Sulfonate-Containing Ester Compositions

Minimally, in some embodiments, the sulfonate-containing esters have anaverage of at least one ester group per sulfonate-containing estermolecule and at least one sulfonate per sulfonate-containing estermolecule. Generally, the sulfonate-containing esters are produced byreacting the herein described sulfonic acid-containing esters with abase. Because the feedstock sulfonic acid-containing esters can comprisea mixture of sulfonic acid-containing ester molecules having differentnumber of ester group and different number of sulfonic acid groups, thenumber of groups present in the sulfonate-containing esters can bediscussed as an average number of groups per sulfonate-containing estermolecule or as an average ratio per sulfonate-containing ester moleculewithin a sulfonate-containing ester composition.

The number of ester groups, the average number of ester groups persulfonate-containing ester molecule, the number of sulfonate groups, theaverage number of sulfonate groups per sulfonate-containing estermolecule are separate elements of the sulfonate-containing ester, thenumber of moiety X³'s, the average number of moiety X³'s, the number ofmoiety Y³'s, the average number of moiety Y³'s, the number of moietyZ³'s, the average number of moiety Z³'s, the number of moiety X⁴'s, theaverage number of moiety X⁴'s, the number of moiety Y⁴'s, the averagenumber of moiety Y⁴'s, the number of moiety Z⁴'s, and the average numberof moiety Z⁴'s. Because the sulfonate-containing esters are producedfrom the sulfonic acid-containing esters, the sulfonate-containingesters can have any number of ester groups or average number of estergroups per sulfonate-containing ester molecule as described for thesulfonic acid-containing ester. The number and identity of the sulfonategroup, moiety X³'s, moiety Y³'s, moiety Z³'s, moiety X⁴'s, moiety Y⁴'s,and moiety Z⁴'s present in the sulfonate-containing esters will befurther described herein.

Minimally, in some embodiments, the sulfonate-containing esters have anaverage of at least one ester group per sulfonate-containing estermolecule and at least one sulfonate group per sulfonate-containing estermolecule. The potential average number of ester groups persulfonate-containing ester molecule have been previously described. Insome embodiments, the sulfonate-containing esters have an average of atleast 1.5 sulfonate groups per sulfonate-containing ester molecule;alternatively, have an average of at least 2 sulfonate groups persulfonate-containing ester molecule; alternatively, an average of atleast 2.5 sulfonate groups per sulfonate-containing ester molecule; oralternatively, an average of at least 3 sulfonate groups persulfonate-containing ester molecule. In other embodiments, thesulfonate-containing esters have an average of from 1.5 to 9 sulfonategroups per sulfonate-containing ester molecule; alternatively, anaverage of from 3 to 8 sulfonate groups per sulfonate-containing estermolecule; alternatively, an average of from 2 to 4 sulfonate groups persulfonate-containing ester molecule; or alternatively, an average offrom 4 to 8 sulfonate acid groups per sulfonate-containing estermolecule.

In another aspect, the sulfonate-containing ester further contains ahydroxy group. In some embodiments, the sulfonate-containing estercomprises an average of at least 1 hydroxy group persulfonate-containing ester molecule.

In another independent aspect, the sulfonate-containing estercomposition comprises an average of at least one ester group persulfonate-containing ester molecule and an average of at least onemoiety X³ per sulfonate-containing ester mole wherein the moiety X³ hasthe structure:

In the moiety X³ structure, Q^(s1) is hydrogen or a hydroxy group,R^(s1) and R^(s2) are independently selected from the consisting ofhydrogen, C₁ to C₂₀ organyl groups, and C₁ to C₂₀ hydrocarbyl groups, Mrepresents a metal atom having an oxidation number n, y ranges from 1 tothe oxidation number n and the unspecified valences of moiety X³represent the remainder of the sulfonate-containing ester molecule.Q^(s1), R^(s1), R^(s2), M, n, and y are separate elements of moiety X³that allow moiety X³ to have any combination of further Q^(s1), R^(s1),R^(s2), M, n, and y elements as described herein. In some particularembodiments, R^(s1) and R^(s2) are hydrogen. In other embodiments, n isan integer ranging from 1 to 3. In one aspect, the metal atom isselected from the group consisting of sodium, potassium, calcium,magnesium, barium, and mixtures thereof. In other aspects, the metalatom is sodium. In yet other aspects, the metal atom is calcium ormagnesium. In yet other aspects, the metal atom is barium.

In particular embodiments, the sulfonate-containing esters have anaverage of at least 1.5 moiety X³'s per sulfonate-containing estermolecule. In other embodiments, the sulfonate-containing esters have anaverage of at least 2 moiety X³'s per sulfonate-containing estermolecule; alternatively, an average of at least 2.5 moiety X³'s persulfonate-containing ester molecule; or alternatively, an average of atleast 3 moiety X³'s per sulfonate-containing ester molecule. In otheraspects, the sulfonate-containing esters have an average of from 1.5 to9 moiety X³'s per sulfonate-containing ester molecule. Alternatively,the sulfonate acid containing ester have an average of from 3 to 8moiety X³'s per sulfonate-containing ester molecule; alternatively, anaverage of from 2 to 4 moiety X³'s per sulfonate-containing estermolecule; or alternatively, an average of from 4 to 8 moiety X³'s persulfonate-containing ester molecule.

In another independent aspect, the sulfonate-containing estercomposition comprises an average of at least one ester group persulfonate-containing ester molecule and an average of at least onemoiety Y³ per sulfonate-containing ester mole wherein the moiety Y³ hasthe structure:

In the moiety Y³ structure, R^(s1) and R^(s2) are independently selectedfrom the consisting of hydrogen, C₁ to C₂₀ organyl groups, and C₁ to C₂₀hydrocarbyl groups, M represents a metal atom having an oxidation numbern, y ranges from 1 to the oxidation number n and the unspecifiedvalences of moiety Y³ represent the remainder of thesulfonate-containing ester molecule. R^(s1), R^(s2), M, n, and y areseparate elements of moiety Y³ that allow moiety Y³ to have anycombination of further R^(s1), R^(s2), M, n, and y elements as describedherein. In some particular embodiments, R^(s1) and R^(s2) are hydrogen.In other embodiments, n is an integer ranging from 1 to 3. In oneaspect, the metal atom is selected from the group consisting of sodium,potassium, calcium, magnesium, barium, and mixtures thereof. In otheraspects, the metal atom is sodium. In yet other aspects, the metal atomis calcium or magnesium. In yet other aspects, the metal atom is barium.

In particular embodiments, the sulfonate-containing esters have anaverage of at least 1.5 moiety Y³'s per sulfonate-containing estermolecule. In other embodiments, the sulfonate-containing esters have anaverage of at least 2 moiety Y³'s per sulfonate-containing estermolecule; alternatively, an average of at least 2.5 moiety Y³'s persulfonate-containing ester molecule; or alternatively, an average of atleast 3 moiety Y³'s per sulfonate acid containing ester molecule. Inother aspects, the sulfonate-containing esters have an average of from1.5 to 9 moiety Y³'s per sulfonate-containing ester molecule.Alternatively, the sulfonate-containing esters have an average of from 3to 8 moiety Y³'s per sulfonate-containing ester molecule; alternatively,an average of from 2 to 4 moiety Y³'s per sulfonate-containing estermolecule; or alternatively, an average of from 4 to 8 moiety Y³'s persulfonate-containing ester molecule.

In another independent aspect, the sulfonate-containing estercomposition comprises an average of at least one ester group persulfonate-containing ester molecule and an average of at least onemoiety Z³ per sulfonate-containing ester mole wherein the moiety Z³ hasthe structure:

In the moiety Z³ structure, R^(s1) and R^(s2) are independently selectedfrom the consisting of hydrogen, C₁ to C₂₀ organyl groups, and C₁ to C₂₀hydrocarbyl groups, M represents a metal atom having an oxidation numbern, y ranges from 1 to the oxidation number n and the unspecifiedvalences of moiety Z³ represent the remainder of thesulfonate-containing ester molecule. R^(s1), R^(s2), M, n, and y areseparate elements of moiety Z³ that allow moiety Z³ to have anycombination of further R^(s1), R^(s2), M, n, and y elements as describedherein. In some particular embodiments, R^(s1) and R^(s2) are hydrogen.In other embodiments, n is an integer ranging from 1 to 3. In oneaspect, the metal atom is selected from the group consisting of sodium,potassium, calcium, magnesium, barium, and mixtures thereof. In otheraspects, the metal atom is sodium. In yet other aspects, the metal atomis calcium or magnesium. In yet other aspects, the metal atom is barium.

In particular embodiments, the sulfonate-containing esters have anaverage of at least 1.5 moiety Z³'s per sulfonate-containing estermolecule. In other embodiments, the sulfonate-containing esters have anaverage of at least 2 moiety Z³'s per sulfonate-containing estermolecule; alternatively, an average of at least 2.5 moiety Z³'s persulfonate-containing ester molecule; or alternatively, an average of atleast 3 moiety Z³'s per sulfonate acid containing ester molecule. Inother aspects, the sulfonate-containing esters have an average of from1.5 to 9 moiety Z³'s per sulfonate-containing ester molecule.Alternatively, the sulfonate-containing esters have an average of from 3to 8 moiety Z³'s per sulfonate-containing ester molecule; alternatively,an average of from 2 to 4 moiety Z³'s per sulfonate-containing estermolecule; or alternatively, an average of from 4 to 8 moiety Z³'s persulfonate-containing ester molecule.

In another independent aspect, the sulfonate-containing estercomposition comprises an average of at least one ester group persulfonate-containing ester molecule and an average of at least onemoiety X⁴ per sulfonate-containing ester mole wherein the moiety X⁴ hasthe structure:

In the moiety X⁴ structure, Q^(s1) is hydrogen or a hydroxy group;R^(s1) and R^(s2) are independently selected from the consisting ofhydrogen, C₁ to C₂₀ organyl groups, and C₁ to C₂₀ hydrocarbyl groups;R^(s3), R^(s4), and R^(s5) are independently selected from hydrogen C₁to C₂₀ organyl groups, and C₁ to C₂₀ hydrocarbyl groups; and theunspecified valences of moiety X⁴ represent the remainder of thesulfonate-containing ester molecule. Q^(s1), R^(s1), R^(s2), R^(s3),R^(s4), and R^(s5) are separate elements of moiety X⁴ that allow moietyX⁴ to have any combination of further Q^(s1), R^(s1), R^(s2), R^(s3),R^(s4), and R^(s5) elements as described herein. In some aspects, thestructure NR^(s3)R^(s4)R^(s5) represents a compound selected from thegroup consisting of a trialkylamine, a dialkylamine, and amonoalkylamine. In some embodiments, NR^(s3)R^(s4)R^(s5) representstriethanolamine. In some particular embodiments, R^(s1) and R^(s2) arehydrogen.

In particular embodiments, the sulfonate-containing esters have anaverage of at least 1.5 moiety X⁴'s per sulfonate-containing estermolecule. In other embodiments, the sulfonate-containing esters have anaverage of at least 2 moiety X⁴'s per sulfonate-containing estermolecule; alternatively, an average of at least 2.5 moiety X⁴'s persulfonate-containing ester molecule; or alternatively, an average of atleast 3 moiety X⁴'s per sulfonate-containing ester molecule. In otheraspects, the sulfonate-containing esters have an average of from 1.5 to9 moiety X⁴'s per sulfonate-containing ester molecule. Alternatively,the sulfonate acid containing ester have an average of from 3 to 8moiety X⁴'s per sulfonate-containing ester molecule; alternatively, anaverage of from 2 to 4 moiety X⁴'s per sulfonate-containing estermolecule; or alternatively, an average of from 4 to 8 moiety X⁴'s persulfonate-containing ester molecule.

In another independent aspect, the sulfonate-containing estercomposition comprises an average of at least one ester group persulfonate-containing ester molecule and an average of at least onemoiety Y⁴ per sulfonate-containing ester mole wherein the moiety

In the moiety Y⁴ structure, R^(s1) and R^(s2) are independently selectedfrom the consisting of hydrogen, C₁ to C₂₀ organyl groups, and C₁ to C₂₀hydrocarbyl groups, R^(s3), R^(s4), and R^(s5) are independentlyselected from hydrogen C₁ to C₂₀ organyl groups, and C₁ to C₂₀hydrocarbyl groups, and the unspecified valences of moiety Y⁴ representthe remainder of the sulfonate-containing ester molecule. R^(s1),R^(s2), R^(s3), R^(s4), and R^(s5) are separate elements of moiety X⁴and thus moiety Y⁴ can have any combination of further R^(s1), R^(s2),R^(s3), R^(s4), and R^(s5) embodiments as described herein. In someaspects, the structure NR^(s3)R^(s4)R^(s5) represents a compoundselected from the group consisting of a trialkylamine, a dialkylamine,and a monoalkylamine. In some embodiments, NR^(s3)R^(s4)R^(s5)represents triethanolamine. In some particular embodiments, R^(s1) andR^(s2) are hydrogen.

In particular embodiments, the sulfonate-containing esters have anaverage of at least 1.5 moiety Y⁴'s per sulfonate-containing estermolecule. In other embodiments, the sulfonate-containing esters have anaverage of at least 2 moiety Y⁴'s per sulfonate-containing estermolecule; alternatively, an average of at least 2.5 moiety Y⁴'s persulfonate-containing ester molecule; or alternatively, an average of atleast 3 moiety Y⁴'s per sulfonate-containing ester molecule. In otheraspects, the sulfonate-containing esters have an average of from 1.5 to9 moiety Y⁴'s per sulfonate-containing ester molecule. Alternatively,the sulfonate acid containing ester have an average of from 3 to 8moiety Y⁴'s per sulfonate-containing ester molecule; alternatively, anaverage of from 2 to 4 moiety Y⁴'s per sulfonate-containing estermolecule; or alternatively, an average of from 4 to 8 moiety Y⁴'s persulfonate-containing ester molecule.

In another independent aspect, the sulfonate-containing estercomposition comprises an average of at least one ester group persulfonate-containing ester molecule and an average of at least onemoiety Z⁴ per sulfonate-containing ester mole wherein the moiety Z⁴ hasthe structure:

In the moiety Z⁴ structure, R^(s1) and R^(s2) are independently selectedfrom the consisting of hydrogen, C₁ to C₂₀ organyl groups, and C₁ to C₂₀hydrocarbyl groups, R^(s3), R^(s4), and R^(s5) are independentlyselected from hydrogen C₁ to C₂₀ organyl groups, and C₁ to C₂₀hydrocarbyl groups, and the unspecified valences of moiety Z⁴ representthe remainder of the sulfonate-containing ester molecule. R^(s1),R^(s2), R^(s3), R^(s4), and R^(s5) are separate elements of moiety Z⁴that allow moiety Z⁴ to have any combination of further R^(s1), R^(s2),R^(s3), R^(s4), and R^(s5) embodiments as described herein. In someaspects, the structure NR^(s3)R^(s4)R^(s5) represents a compoundselected from the group consisting of a trialkylamine, a dialkylamine,and a monoalkylamine. In some embodiments, NR^(s3)R^(s4)R^(s5)represents triethanolamine. In some particular embodiments, R^(s1) andR^(s2) are hydrogen.

In particular embodiments, the sulfonate-containing esters have anaverage of at least 1.5 moiety Z⁴'s per sulfonate-containing estermolecule. In other embodiments, the sulfonate-containing esters have anaverage of at least 2 moiety Z⁴'s per sulfonate-containing estermolecule; alternatively, an average of at least 2.5 moiety Z⁴'s persulfonate-containing ester molecule; or alternatively, an average of atleast 3 moiety Z⁴'s per sulfonate-containing ester molecule. In otheraspects, the sulfonate-containing esters have an average of from 1.5 to9 moiety Z⁴'s per sulfonate-containing ester molecule. Alternatively,the sulfonate acid containing ester have an average of from 3 to 8moiety Z⁴'s per sulfonate-containing ester molecule; alternatively, anaverage of from 2 to 4 moiety Z⁴'s per sulfonate-containing estermolecule; or alternatively, an average of from 4 to 8 moiety Z⁴'s persulfonate-containing ester molecule.

In some embodiments, there is provided a sulfonate-containing estermolecule comprising at least one ester group and at least one sulfonategroup. The number of ester groups and the number of sulfonate groups areseparate elements and the sulfonate-containing ester molecule cancontain any number of ester groups and sulfonate groups as describedherein.

In some embodiments, the sulfonate-containing ester molecule comprisesat least 2 ester groups. Alternatively, in some embodiments, thesulfonate-containing ester molecule comprises at least 3 ester groups.In one aspect, the sulfonate-containing ester molecule comprises from 2to 9 ester groups. In one aspect, the sulfonate-containing estermolecule comprises from 2 to 8 ester groups; alternatively, from 2 to 7ester groups; alternatively, from 3 to 5 ester groups; or alternatively,from 3 to 4 ester groups. In yet other embodiments, thesulfonate-containing ester molecule comprises 3 ester groups oralternatively, comprises 4 ester groups.

In further embodiments, the sulfonate-containing ester moleculecomprises at least one sulfonate group. In other embodiments, thesulfonate-containing ester molecule comprises at least 2 sulfonategroups; or alternatively, at least 3 sulfonate groups. In otherembodiments, the sulfonate-containing ester molecule comprises from 2 to9 sulfonate groups; alternatively, from 3 to 8 sulfonate groups;alternatively, from 2 to 4 sulfonate groups; or alternatively, from 4 to8 sulfonate groups.

In some embodiments, the sulfonate-containing ester molecule comprisesat least one ester group and a least one moiety X³. In some embodiments,the sulfonate-containing ester molecule comprising ester groups andmoiety X³ can comprise any combination of the number of ester groups andany number of moiety X³'s as described herein. The number of estergroups within the within the sulfonate-containing ester moleculecomprising ester groups and moiety X³ has been described previously. Infurther embodiments, the sulfonate-containing ester molecule comprisingester groups and moiety X³ can at least 2 moiety X³'s, or alternatively,at least 3 moiety X³'s. In other embodiments, the sulfonate-containingester molecule comprising ester groups and moiety X³ comprises from 2 to9 moiety X³'s; alternatively, from 3 to 8 moiety X³'s; alternatively,from 2 to 4 moiety X³'s; or alternatively, from 4 to 8 moiety X³'s.

In some embodiments, the sulfonate-containing ester molecule comprisesat least one ester group and a least one moiety Y³. In some embodiments,the sulfonate-containing ester molecule comprising ester groups andmoiety Y³ can comprise any combination of the number of ester groups andany number of moiety Y³'s as described herein. The number of estergroups within the within the sulfonate-containing ester moleculecomprising ester groups and moiety Y³ has been described previously. Infurther embodiments, the sulfonate-containing ester molecule comprisingester groups and moiety Y³ can at least 2 moiety Y³'s, or alternatively,at least 3 moiety Y³'s. In other embodiments, the sulfonate-containingester molecule comprising ester groups and moiety Y³ comprises from 2 to9 moiety Y³'s; alternatively, from 3 to 8 moiety Y³'s; alternatively,from 2 to 4 moiety Y³'s; or alternatively, from 4 to 8 moiety Y³'s.

In some embodiments, the sulfonate-containing ester molecule comprisesat least one ester group and a least one moiety Z³. In some embodiments,the sulfonate-containing ester molecule comprising ester groups andmoiety Z³ can comprise any combination of the number of ester groups andany number of moiety Z³'s as described herein. The number of estergroups within the within the sulfonate-containing ester moleculecomprising ester groups and moiety Z³ has been described previously. Infurther embodiments, the sulfonate-containing ester molecule comprisingester groups and moiety Z³ can at least 2 moiety Z³'s, or alternatively,at least 3 moiety Z³'s. In other embodiments, the sulfonate-containingester molecule comprising ester groups and moiety Z³ comprises from 2 to9 moiety Z³'s; alternatively, from 3 to 8 moiety Z³'s; alternatively,from 2 to 4 moiety Z³'s; or alternatively, from 4 to 8 moiety Z³'s.

In some embodiments, the sulfonate-containing ester molecule comprisesat least one ester group and a least one moiety X⁴. In some embodiments,the sulfonate-containing ester molecule comprising ester groups andmoiety X⁴ can comprise any combination of the number of ester groups andany number of moiety X⁴'s as described herein. The number of estergroups within the within the sulfonate-containing ester moleculecomprising ester groups and moiety X⁴ has been described previously. Infurther embodiments, the sulfonate-containing ester molecule comprisingester groups and moiety X⁴ can at least 2 moiety X⁴'s, or alternatively,at least 3 moiety X⁴'s. In other embodiments, the sulfonate-containingester molecule comprising ester groups and moiety X⁴ comprises from 2 to9 moiety X⁴'s; alternatively, from 3 to 8 moiety X⁴'s; alternatively,from 2 to 4 moiety X⁴'s; or alternatively, from 4 to 8 moiety X⁴'s.

In some embodiments, the sulfonate-containing ester molecule comprisesat least one ester group and a least one moiety Y⁴. In some embodiments,the sulfonate-containing ester molecule comprising ester groups andmoiety Y⁴ can comprise any combination of the number of ester groups andany number of moiety Y⁴'s as described herein. The number of estergroups within the within the sulfonate-containing ester moleculecomprising ester groups and moiety Y⁴ has been described previously. Infurther embodiments, the sulfonate-containing ester molecule comprisingester groups and moiety Y⁴ can at least 2 moiety Y⁴'s, or alternatively,at least 3 moiety Y⁴'s. In other embodiments, the sulfonate-containingester molecule comprising ester groups and moiety Y⁴ comprises from 2 to9 moiety Y⁴'s; alternatively, from 3 to 8 moiety Y⁴'s; alternatively,from 2 to 4 moiety Y⁴'s; or alternatively, from 4 to 8 moiety Y⁴'s.

In some embodiments, the sulfonate-containing ester molecule comprisesat least one ester group and a least one moiety Z⁴. In some embodiments,the sulfonate-containing ester molecule comprising ester groups andmoiety Z⁴ can comprise any combination of the number of ester groups andany number of moiety Z⁴'s as described herein. The number of estergroups within the within the sulfonate-containing ester moleculecomprising ester groups and moiety Z⁴ has been described previously. Infurther embodiments, the sulfonate-containing ester molecule comprisingester groups and moiety Z⁴ can at least 2 moiety Z⁴'s, or alternatively,at least 3 moiety Z⁴'s. In other embodiments, the sulfonate-containingester molecule comprising ester groups and moiety Z⁴ comprises from 2 to9 moiety Z⁴'s; alternatively, from 3 to 8 moiety Z⁴'s; alternatively,from 2 to 4 moiety Z⁴'s; or alternatively, from 4 to 8 moiety Z⁴'s.

The sulfonate-containing ester oil compositions may also be described asa product produced by the process comprising contacting a sulfonicacid-containing ester with a base and may be further limited by theprocess as described herein.

Process for Making a Thiol Ester Composition

The present invention advantageously provides processes for producing athiol ester composition as embodiments of the present invention. As anembodiment, the present invention advantageously includes a process toproduce a thiol ester composition by contacting hydrogen sulfide and anunsaturated ester composition containing unsaturated esters and reactingthe hydrogen sulfide and unsaturated esters to form or produce the thiolester composition. As another embodiment of the present invention, aprocess to produce the thiol ester composition is advantageouslyprovided. In this embodiment, the process includes contacting acomposition comprising a polyol with a composition comprising a thiolcontaining carboxylic acid composition and reacting the polyol and thiolcontaining carboxylic acid composition to form the thiol estercomposition.

In some embodiments of the present invention that include producingthiol ester compositions, the unsaturated ester composition is a naturalsource oil. In an aspect, the unsaturated ester composition is soybeanoil or alternatively castor oil. Other suitable types of unsaturatedester compositions are described herein and can be used in the processesfor producing the thiol ester compositions.

Thiol Esters from Unsaturated Esters

As an embodiment of the present invention, the thiol esters describedherein can be produced by a process comprising contacting hydrogensulfide and an unsaturated ester composition and reacting hydrogensulfide and the unsaturated ester composition to form the thiol estercomposition. In one embodiment, the unsaturated ester compositionincludes unsaturated esters having an average of at least 1.5 estergroups and an average of at least 1.5 carbon-carbon double bonds perunsaturated ester molecule. In this embodiment, the thiol estercomposition includes thiol ester molecules having a molar ratio ofcyclic sulfides to thiol groups of less than 1.5.

The processes for producing the thiol ester composition can be appliedto any of the unsaturated esters described herein and used to produceany of the thiol esters described herein. The process for producing thethiol ester composition can also include any additional process steps orprocess conditions described herein.

In some aspects, the reaction between hydrogen sulfide and theunsaturated ester occurs in the presence of a solvent. In other aspects,the reaction between the unsaturated ester and hydrogen sulfide occursin the substantial absence of a solvent. When the solvent is present,the solvent can be selected from the group consisting of an aliphatichydrocarbon, an ether, an aromatic compound, an alcohol, or combinationsthereof. In further embodiments, the solvent can be an aliphatichydrocarbon, an ether, or an aromatic compound. Generally, the solvent,regardless of its chemical class, includes from 1 to 20 carbon atoms; oralternatively, from 3 to 10 carbon atoms. When the solvent includes analiphatic solvent, the aliphatic solvent is butane, isobutane, pentane,hexane, heptane, octane, or any mixture thereof. When the solventincludes an aromatic solvent, the aromatic solvent is benzene, toluene,xylene, ethylbenzene, or any mixtures thereof. When the solvent includesan alcohol, the alcohol is methanol, 1-propanol, 2-propanol, 1-butanol,2-butanol, 2-methyl-2-propanol, or mixtures thereof. When the solventincludes an ether, the ether is diethyl ether, dipropyl ether,tetrahydrofuran, or mixtures thereof. Other types of suitable solventswill be apparent to those of skill in the art and are to be consideredwithin the scope of the present invention.

When a solvent is used for the reaction between the unsaturated esterand hydrogen sulfide, the quantity of solvent can be any amount thatfacilitates the reaction. In some embodiments, the mass of the solventis less than 30 times the mass of the unsaturated ester. In otherembodiments, the mass of the solvent is less than 20 times the mass ofthe unsaturated ester; alternatively, less than 15 times the mass of theunsaturated ester; alternatively, less than 10 times the mass of theunsaturated ester; or alternatively, less than 5 times the mass of theunsaturated ester. In other embodiments, the mass of the solvent is from2 times to 20 times the mass of the unsaturated ester; alternatively,from 3 times to 15 times the mass of the unsaturated ester;alternatively, 4 times to 15 times the mass of the unsaturated ester; oralternatively, from 5 times to 10 times the mass of the unsaturatedester.

The hydrogen sulfide to molar equivalents of unsaturated estercarbon-carbon double bonds molar ratio utilized in the process toproduce the thiol ester composition can be any molar ratio that producesthe desired thiol ester. The molar equivalents of unsaturated estercarbon-carbon double bonds is calculated by the equation:

${\frac{{UES}\mspace{14mu}{Mass}}{{UES}\mspace{14mu}{GMW}} \times {UES}\mspace{14mu} C} = C$In this equation, UES GMW is the average gram molecular weight of theunsaturated ester, UES Mass is the mass of the feedstock unsaturatedester, and UES C═C is the average number of double bonds per unsaturatedester molecule. In some embodiments, the thiol ester molecules have amolar ratio of the hydrogen sulfide to the unsaturated estercarbon-carbon double bonds of greater than 2. In other embodiments, thehydrogen sulfide to unsaturated ester carbon-carbon double bonds molarratio is greater than 5; alternatively, greater than 10; alternatively,greater than 15; or alternatively, greater than 20. In otherembodiments, the hydrogen sulfide to unsaturated ester carbon-carbondouble bonds molar ratio can be from 2 to 500; alternatively, from 5 to200; alternatively, from 10 to 100; or alternatively, from 100 to 200.

In some aspects the reaction between the unsaturated ester and hydrogensulfide is catalyzed. In some embodiments, the reaction of theunsaturated ester and hydrogen sulfide can be catalyzed by aheterogeneous catalyst or a homogeneous catalyst. In other embodiments,the reaction of the unsaturated ester and hydrogen sulfide is initiatedby a free radical initiator or ultraviolet (UV) radiation. Othersuitable catalyzing and initiating methods will be apparent to those ofskill in the art and are to be considered within the scope of thepresent invention.

The heterogeneous catalyst is selected from the group consisting of acidclays (such as Filtrol®-24, which is commercially available fromEnglehard), acid zeolites (such as LZY-84, which is commerciallyavailable from UOP), cobalt/molybdenum oxide supported catalysts (suchas TK-554, which is commercially available from Haldor-Topsoe), andnickel/molybdenum supported oxide catalysts (such as TK-573, which iscommercially available from Haldor-Topsoe). The homogeneous catalyst ismethane sulfonic acid or toluene sulfonic acid. Other suitable types ofheterogeneous and homogeneous catalysts will be apparent to those ofskill in the art and are to be considered within the scope of thepresent invention.

The free radical initiator can be any free radical initiator capable offorming free radical under thermal or light photolysis. Generally, thefree radical initiator is selected from the general class compoundshaving a —N═N— group or a —O—group. Specific classes of free radicalinitiators include diazo compounds, dialkyl peroxides, hydroperoxides,and peroxy esters. Specific initiators include azobenzene,2,2′-azobis(2-methylpropionitrile, 4,4′-azobis(4-cyanovaleric acid),1,1′-azobis(cyclohexanecarbo-nitrile), 2,2′-azobis(2-methylpropane),2,2′-azobis(2-methylpropionamidine) dihydro-chloride,methylpropionitrile, azodicarboxamide, tert-butyl hydroperoxide,di-tert-butyl peroxide, octylperbenzoate. In some embodiments, the freeradical initiated reaction is performed at a reaction temperature within±50° C. of the 1 hour half life of the free radical initiator. In otherembodiments, the free radical initiated reaction is performed at areaction temperature within ±25° C. of the 1 hour half life of the freeradical initiator; alternatively, at a reaction temperature within ±20°C. of the 1 hour half life of the free radical initiator; alternatively,at a reaction temperature within ±15° C. of the 1 hour half life of thefree radical initiator; alternatively, at a reaction temperature within±10° C. of the 1 hour half life of the free radical initiator. Inembodiments, wherein the free radical initiator catalyst reaction of theunsaturated ester and hydrogen sulfide is initiated by light photolysis,the light can be any light capable of creating free radicals. In someembodiments the light is UV radiation.

In another aspect, the reaction of the unsaturated ester and hydrogensulfide is initiated by UV radiation. In these embodiments, the UVradiation can be any UV radiation capable of initializing the reactionof the unsaturated ester and hydrogen sulfide. In some embodiments, theUV radiation is generated by a medium pressure mercury lamp. Although UVradiation has been described as the light source, other suitable typesof light sources will be apparent to those of skill in the art and areto be considered within the scope of the present invention.

The reaction of the unsaturated ester and hydrogen sulfide can occur ina batch reactor or a continuous reactor. Example continuous reactorsinclude continuous stirred reactors, fixed bed reactors, and the like.Example batch reactors include UV batch reactors. Other types of batchand continuous reactors that can be used in embodiments of the presentinvention will be apparent to those of skill in the art and are to beconsidered within the scope of the present invention.

When a continuous reactor is used, a feed unsaturated ester weighthourly space velocity ranging from 0.1 to 5 can be used to produce thedesired thiol ester. Alternatively, the feed unsaturated ester weighthourly space velocity ranges between 0.1 to 5; alternatively, from 0.1to 2. Alternatively, the feed unsaturated ester weight hourly spacevelocity is 0.1; alternatively, the feed unsaturated ester weight hourlyspace velocity is 0.25; or alternatively, the feed unsaturated esterweight hourly space velocity is 2.

The time required for the reaction of the unsaturated ester and hydrogensulfide can be any time required to form the described thiol ester.Generally, the time required for the reaction of the unsaturated esterand hydrogen sulfide is at least 5 minutes. In some embodiments, thetime required for the reaction of the unsaturated ester and hydrogensulfide ranges from 5 minutes to 72 hours; alternatively, from 10minutes to 48 hours; or alternatively, from 15 minutes to 36 hours.

In embodiments, the process to produce the thiol ester further comprisesa step to remove excess or residual hydrogen sulfide after reacting thehydrogen sulfide and the unsaturated ester composition. In someembodiments, the thiol ester is vacuum stripped. In some embodiments,the thiol ester is vacuum stripped at a temperature ranging between 25°C. and 250° C.; or alternatively, between 50° C. and 200° C. In otherembodiments, the thiol ester is sparged with an inert gas to removehydrogen sulfide. In some embodiments, the thiol ester is sparged withan inert gas at a temperature between 25° C. and 250° C.; oralternatively, between 50° C. and 200° C. In some aspects, the inert gasis nitrogen. Generally, the stripped or sparged thiol ester comprisesless than 0.1 weight percent hydrogen sulfide. In other embodiments, thestripped or sparged thiol ester comprises less than 0.05 weight percentsulfur; alternatively, less than 0.025 weight percent hydrogen sulfide;or alternatively, less than 0.01 weight percent hydrogen sulfide

The reaction between the unsaturated ester and hydrogen sulfide can beperformed at any temperature capable of forming the thiol ester. In someembodiments, the unsaturated ester and hydrogen sulfide can be reactedat a temperature greater than −20° C. In other embodiments, theunsaturated ester and hydrogen sulfide can be reacted at a temperaturegreater than 0° C.; alternatively, greater than 20° C.; alternatively,greater than 50° C.; alternatively, greater than 80° C.; oralternatively, greater than 100° C. In yet other embodiments, theunsaturated ester and hydrogen sulfide can be reacted at a temperaturefrom −20° C. to 200° C.; alternatively, from 120° C. to 240° C.;alternatively, from 170° C. to 210° C.; alternatively, from 185° C. to195° C.; alternatively, from 20° C. to 200° C.; alternatively, from 20°C. to 170° C.; or alternatively, from 80° C. to 140° C.

The reaction between the unsaturated ester and hydrogen sulfide can beperformed at any pressure that maintains a portion of the hydrogensulfide in a liquid state. In some embodiments the unsaturated ester andhydrogen sulfide reaction can be performed at a pressure ranging from100 psig to 2000 psig. In other embodiments, the unsaturated ester andhydrogen sulfide reaction can be performed at a pressure ranging from150 to 1000 psig; or alternatively, from 200 to 600 psig.

Thiol esters having a low cyclic sulfide content can be produced usingthe disclosed process. In an aspect, the process for producing the thiolester forms or produces a thiol ester having a molar ratio of cyclicsulfide to thiol groups of less than 1.5. Additional cyclic sulfide tothiol groups molar ratios are disclosed herein.

In addition to lower cyclic sulfide content, thiol esters having a lowcarbon-carbon double bond to thiol group molar ratio can also beproduced using the disclosed process. In an aspect, the processdescribed herein produces the thiol ester having a carbon-carbon doublebond to thiol group molar ratio of less than 1.5. Additionalcarbon-carbon double bond to thiol group molar ratios are disclosedherein.

In some aspects, the process described herein produces the thiol estermolecules having an average of greater than 5 weight percent thiolsulfur. Additional thiol sulfur contents are disclosed herein. In otheraspects, the process for producing a thiol ester forms a thiol esterhaving greater than 40 percent of the thiol ester total side chainsinclude sulfur. Other percentages of the thiol ester total side chainsthat include sulfur are disclosed herein.

In some embodiments, the process for producing a thiol ester compositionincludes contacting an unsaturated ester and hydrogen sulfide andreacting the unsaturated ester and the hydrogen sulfide to form a thiolester. The thiol ester comprises thiol ester molecules that have a ratioof cyclic sulfide to thiol groups of less than 1.5.

Thiol Ester from a Polyol and a Thiol Containing Carboxylic AcidDerivative

As another embodiment of the present invention, another process toproduce the thiol ester composition is advantageously provided. In thisembodiment, the process includes the steps of contacting a compositioncomprising a polyol with a composition comprising a thiol containingcarboxylic acid and/or thiol containing carboxylic acid derivative andreacting the polyol and thiol containing carboxylic acid and/or thiolcontaining carboxylic acid derivative to produce the thiol estercomposition. This process can be applied to any polyol, thiol containingcarboxylic acid, or thiol containing carboxylic acid derivativedescribed herein. The process for producing the thiol ester compositioncan also include any additional process steps or process conditionsdescribed herein. Additionally, the process for producing the thiolester composition can form any thiol ester described herein.

In some embodiments, the thiol ester composition includes thiol estermolecules that have an average of at least 1.5 ester groups and anaverage of at least 1.5 thiol groups per thiol ester molecule.

The polyol used to produce the thiol ester by contacting a polyol and athiol carboxylic acid and/or thiol carboxylic acid equivalent (forexample a thiol carboxylic acid methyl ester) can be any polyol ormixture of polyols that can produce the described thiol containingester.

In one aspect, the polyol used to produce the thiol ester can comprisefrom 2 to 20 carbon atoms. In other embodiments, the polyol comprisesfrom 2 to 10 carbon atoms; alternatively from 2 to 7 carbon atoms;alternatively from 2 to 5 carbon atoms. In further embodiments, thepolyol may be a mixture of polyols having an average of 2 to 20 carbonatoms; alternatively, an average of from 2 to 10 carbon atoms;alternatively, an average of 2 to 7 carbon atoms; alternatively anaverage of 2 to 5 carbon atoms.

In another aspect, the polyol used to produce the thiol ester can haveany number of hydroxy groups needed to produce the thiol ester asdescribed herein. In some embodiments, the polyol has 2 hydroxy groups;alternatively 3 hydroxy groups; alternatively, 4 hydroxy groups;alternatively, 5 hydroxy groups; or alternatively, 6 hydroxy groups. Inother embodiments, the polyol comprises at least 2 hydroxy groups;alternatively at least 3 hydroxy groups; alternatively, at least 4hydroxy groups; or alternatively, at least 5 hydroxy groups; at least 6hydroxy groups. In yet other embodiments, the polyol comprises from 2 to8 hydroxy groups; alternatively, from 2 to 4 hydroxy groups; oralternatively from 4 to 8 hydroxy groups.

In further aspects, the polyol used to produce the thiol ester is amixture of polyols. In an embodiment, the mixture of polyols has anaverage of at least 1.5 hydroxy groups per polyol molecule. In otherembodiments, the mixture of polyols has an average of at least 2 hydroxygroups per polyol molecule; alternatively, an average of at least 2.5hydroxy groups per polyol molecule; alternatively, an average of atleast 3.0 hydroxy groups per polyol molecule; or alternatively, anaverage of at least 4 hydroxy groups per polyol molecule. In yet anotherembodiments, the mixture of polyols has an average of 1.5 to 8 hydroxygroups per polyol molecule; alternatively, an average of 2 to 6 hydroxygroups per polyol molecule; alternatively, an average of 2.5 to 5hydroxy groups per polyol molecule; alternatively, an average of 3 to 4hydroxy groups per polyol molecule; alternatively, an average of 2.5 to3.5 hydroxy groups per polyol molecule; or alternatively, an average of2.5 to 4.5 hydroxy groups per polyol molecule.

In yet another aspect, the polyol or mixture of polyols used to producethe thiol ester has a molecular weight or average molecular weight lessthan 500. In other embodiments, the polyol or mixture of polyols have amolecular weight or average molecular weight less than 300;alternatively less than 200; alternatively, less than 150; oralternatively, less than 100.

The thiol carboxylic acid and/or thiol carboxylic acid equivalent usedto produce the thiol ester by contacting a polyol and a thiol carboxylicacid and/or thiol carboxylic acid equivalent can be any thiol carboxylicacid mixture comprising thiol carboxylic acids, thiol carboxylic acidequivalent or mixture comprising thiol carboxylic acid equivalents thatcan produce the described thiol containing ester. When talking about thecharacteristics thiol carboxylic acid equivalent or thiol carboxylicacid equivalents, properties such as number of carbon atoms, averagenumber of carbon atom, molecular weight or average molecular weight,number of thiol group, and average number of thiol groups, one willunderstand the these properties will apply to the portion of the thiolcarboxylic acid equivalent which adds to the polyol to form the thiolester.

In an aspect, the thiol carboxylic acid and/or thiol carboxylic acidequivalent used to produce the thiol ester comprises from 2 to 28 carbonatoms. In an embodiment, the thiol carboxylic acid and/or thiolcarboxylic acid equivalent comprises from 4 to 26 carbon atoms;alternatively, from 8 to 24 carbon atoms; alternatively, from 12 to 24carbon atoms; or alternatively, from 14 to 20 carbon atoms. In otherembodiments, a mixture comprising thiol carboxylic acid and/or mixturecomprising thiol carboxylic acid equivalents has an average of 2 to 28carbon atoms per carboxylic acid and/or carboxylic acid equivalent;alternatively, from 4 to 26 carbon atoms per carboxylic acid and/orcarboxylic acid equivalent; alternatively, from 8 to 24 carbon atoms percarboxylic acid and/or carboxylic acid equivalent; alternatively, from12 to 24 carbon atoms per carboxylic acid and/or carboxylic acidequivalent; or alternatively, from 14 to 20 carbon atoms per carboxylicacid and/or carboxylic acid equivalent.

In another aspect, the thiol carboxylic acid and/or thiol carboxylicacid equivalent used to produce the thiol ester has at least 1 thiolgroup; alternatively 2 thiol groups. In some embodiments, a mixturecomprising thiol carboxylic acid and/or mixture comprising thiolcarboxylic acid equivalents has an average of from 0.5 to 3 thiol groupsper carboxylic acid and/or carboxylic acid equivalent; alternatively, anaverage of from 1 to 2 thiol groups per carboxylic acid and/orcarboxylic acid equivalent.

In another aspect, the thiol carboxylic acid and/or thiol carboxylicacid equivalent used to produce the thiol ester has a molecular weightgreater than 100; alternatively greater than 180; alternatively greaterthan 240; or alternatively greater than 260. In other embodiments, thethiol carboxylic acid and/or thiol carboxylic acid equivalent has amolecular weight from 100 to 500; alternatively, from 120 to 420;alternatively, from 180 to 420; alternatively, from 240 to 420; amixture or alternatively, from 260 to 360. In some embodiments, amixture comprising thiol carboxylic acid and/or mixture comprising thiolcarboxylic acid equivalents has an average molecular weight greater than100 per carboxylic acid and/or carboxylic acid equivalent; alternativelygreater than 180 per carboxylic acid and/or carboxylic acid equivalent;alternatively greater than 240 per carboxylic acid and/or carboxylicacid equivalent; or alternatively greater than 260 per carboxylic acidand/or carboxylic acid equivalent. In yet other embodiments, the mixturecomprising of thiol carboxylic acid and/or mixture comprising thiolcarboxylic acid equivalents has an average molecular weight from 100 to500 per carboxylic acid and/or carboxylic acid equivalent;alternatively, from 120 to 420 per carboxylic acid and/or carboxylicacid equivalent; alternatively, from 180 to 420 per carboxylic acidand/or carboxylic acid equivalent; alternatively, from 240 to 420 percarboxylic acid and/or carboxylic acid equivalent; a mixture oralternatively, from 260 to 360 per carboxylic acid and/or carboxylicacid equivalent.

In some aspects, the reaction between the polyol and the thiolcontaining carboxylic acid and/or thiol containing carboxylic acidderivative occurs in the presence of a solvent. In other aspects thereaction between the polyol and the thiol containing carboxylic acidand/or thiol containing carboxylic acid derivative occurs in thesubstantial absence of a solvent. In aspects wherein the reactionbetween the polyol and the thiol containing carboxylic acid and/or thiolcontaining carboxylic acid derivative occurs in the presence of asolvent, the solvent is selected from the group consisting of analiphatic hydrocarbon, an ether, an aromatic compound, or anycombination thereof. Generally, the solvent, regardless of its chemicalclass, can include from 1 to 20 carbon atoms; or alternatively, from 3to 10 carbon atoms. When the solvent includes the aliphatic hydrocarbon,the aliphatic hydrocarbon is butane, isobutane, pentane, hexane,heptane, octane, or any mixture thereof. When the solvent includes thearomatic compound, the aromatic compound is benzene, toluene, xylene,ethylbenzene, or any mixture thereof. When the solvent includes theether, the ether is diethyl ether, dipropyl ether, tetrahydrofuran, andany mixture thereof.

When a solvent is used for the reaction between the polyol and the thiolcontaining carboxylic acid and/or thiol containing carboxylic acidderivative, the quantity of solvent can be any amount that facilitatesthe reaction. In some embodiments, the mass of the solvent is less than30 times the mass of the thiol containing carboxylic acid and/or thiolcontaining carboxylic acid derivative. In other embodiments, the mass ofthe solvent is less than 20 times the mass of the unsaturated ester oil;alternatively, less than 15 times the mass of the thiol containingcarboxylic acid and/or thiol containing carboxylic acid derivative;alternatively, less than 10 times the mass of the thiol containingcarboxylic acid and/or thiol containing carboxylic acid derivative; oralternatively, less than 5 times the mass of the thiol containingcarboxylic acid and/or thiol containing carboxylic acid derivative. Inother embodiments, the mass of the solvent is from 2 times to 20 timesthe mass of the thiol containing carboxylic acid and/or thiol containingcarboxylic acid derivative; alternatively, from 3 times to 15 times themass of the thiol containing carboxylic acid and/or thiol containingcarboxylic acid derivative; or alternatively, from 5 times to 10 timesthe mass of the thiol containing carboxylic acid and/or thiol containingcarboxylic acid derivative.

The equivalent of thiol containing carboxylic acid and/or thiolcontaining carboxylic acid derivative carboxylic acid groups toequivalents of polyol hydroxy groups molar ratio (hereinafter“carboxylic acid group to polyol hydroxy group molar ratio”) utilized inthe process to produce the thiol ester composition can be any carboxylicacid group to polyol hydroxy group molar ratio that produces the desiredthiol ester composition. In some embodiments, the carboxylic acid groupto polyol hydroxy group molar ratio is greater than 0.4. In otherembodiments, the carboxylic acid group to polyol hydroxy group molarratio is greater than 0.6; alternatively, greater than 0.8;alternatively, greater than 1; or alternatively, greater than 1.1. Inother embodiments, the carboxylic acid group to polyol hydroxy groupmolar ratio can range from 0.4 to 1.3; alternatively, from 0.6 to 1.2,or alternatively, from 0.8 to 1.1.

In some aspects, the reaction between the polyol and the thiolcontaining carboxylic acid and/or thiol containing carboxylic acidderivative is catalyzed. In some embodiments, the catalyst is a mineralacid, such as sulfuric or phosphoric acid. In other embodiments, thecatalyst is an organic acid. In embodiments, for example, the organicacid is methane sulfonic acid or toluene sulfonic acid. Other suitabletypes of catalyst will be apparent to those of skill in the art and areto be considered within the scope of the present invention.

The reaction of the polyol and the thiol containing carboxylic acidand/or thiol containing carboxylic acid derivative can occur in a batchreactor or a continuous reactor, as described herein. The reactionbetween the polyol and the thiol containing carboxylic acid and/or thiolcontaining carboxylic acid derivative can be performed at anytemperature capable of forming the thiol ester. In some embodiments, thepolyol and the thiol containing carboxylic acid and/or thiol containingcarboxylic acid derivative can be reacted at a temperature greater than20° C. In other embodiments, the polyol and the thiol containingcarboxylic acid and/or thiol containing carboxylic acid derivative canbe reacted at a temperature greater than 50° C.; alternatively, greaterthan 75° C.; or alternatively, greater than 100° C. In yet otherembodiments, the polyol and the thiol containing carboxylic acid and/orthiol containing carboxylic acid derivative can be reacted at atemperature from 20° C. to 250° C.; alternatively, from 50° C. to 200°C.; alternatively, from 75° C. to 175° C.; or alternatively, from 100°C. to 150° C.

The time required for the reaction of the polyol and the thiolcontaining carboxylic acid and/or thiol containing carboxylic acidderivative can be any time required to form the described thiol esteroil. Generally, the reaction time of the polyol and the thiol containingcarboxylic acid and/or thiol containing carboxylic acid derivative is atleast 5 minutes. In some embodiments, the reaction time is at least 30minutes; alternatively, at least 1 hour; or alternatively, at least 2hours. In yet other embodiments, the reaction time ranges from 5 minutesto 72 hours; alternatively, from 30 minutes to 48 hours; alternatively,from 1 hour minutes to 36 hours; or alternatively, from 2 hours and 24hours.

When a continuous reactor is used, a feed polyol weight unsaturatedester weight hourly space velocity ranging from 0.1 to 5 can be used toproduce the desired thiol ester. Alternatively, the feed polyol weighthourly space velocity ranges between 0.1 to 5; alternatively, from 0.1to 2. Alternatively, the feed polyol ester weight hourly space velocityis 0.1; alternatively, the feed polyol weight hourly space velocity is0.25; or alternatively, the feed polyol weight hourly space velocity is2.

The reaction between the polyol and the thiol containing carboxylic acidand/or thiol containing carboxylic acid derivative can be performed atany reaction pressure that maintains the polyol and the thiol containingcarboxylic acid and/or thiol containing carboxylic acid derivative in aliquid state. In some embodiments, the reaction between the polyol andthe thiol containing carboxylic acid and/or thiol containing carboxylicacid derivative is performed at a pressure ranging from 0 psia to 2000psia. In other embodiments, the reaction pressure ranges from 0 psia to1000 psia; alternatively, from 0 psia and 500 psia; or alternatively, 0psia to 300 psia.

In some embodiments, the process to produce the thiol ester by reactinga polyol and the thiol containing carboxylic acid and/or thiolcontaining carboxylic acid derivative can further include a step toremove excess or residual polyol, thiol containing carboxylic acid,and/or thiol containing carboxylic acid derivative once the polyol hasreacted with the thiol containing carboxylic acid or thiol containingcarboxylic acid derivative. In some embodiments, the thiol ester isvacuum stripped. In some embodiments, the thiol ester is vacuum strippedat a temperature ranging between 25° C. and 250° C.; or alternatively,between 50° C. and 200° C. In other embodiments, the thiol ester issparged with an inert gas to remove excess polyol, thiol containingcarboxylic acid, and/or thiol containing carboxylic acid derivative. Insome embodiments, the thiol ester is sparged with an inert gas at atemperature between 25° C. and 250° C.; or alternatively, between 50° C.and 200° C. In some aspects, the inert gas is nitrogen. Generally, thestripped or sparged thiol ester comprises less than 5 excess polyol,thiol containing carboxylic acid, or thiol containing carboxylic acidderivative. In other embodiments, the stripped or sparged thiol estercomprises less than 2 weight percent excess polyol, thiol containingcarboxylic acid, and/or thiol containing carboxylic acid derivative;alternatively, less than 1 weight percent excess polyol, thiolcontaining carboxylic acid, and/or thiol containing carboxylic acidderivative; or alternatively, less than 0.5 weight percent excesspolyol, thiol containing carboxylic acid, and/or thiol containingcarboxylic acid derivative.

Process for Making Hydroxy Thiol Ester Composition

The present invention advantageously provides processes for producing ahydroxy thiol ester as embodiments of the present invention. As anembodiment, the present invention includes a process to produce thehydroxy thiol ester. The process comprises the steps of contactinghydrogen sulfide and an epoxidized unsaturated ester composition andreacting the hydrogen sulfide and the epoxidized unsaturated ester toform the hydroxy thiol ester. As another embodiment of the presentinvention, another process to produce the hydroxy thiol ester isprovided. In this embodiment, the process comprises the steps ofcontacting a composition comprising a polyol with a compositioncomprising an hydroxy thiol containing carboxylic acid or an hydroxythiol containing carboxylic acid derivative and reacting the polyol andthe hydroxy thiol containing carboxylic acid or the hydroxy thiolcontaining carboxylic acid derivative to form the hydroxy thiol ester.

Hydroxy Thiol Ester from Hydrogen Sulfide and an Epoxidized UnsaturatedEster Composition

As an embodiment of the present invention, the hydroxy thiol estercomposition is produced by a process comprising the steps of contactinghydrogen sulfide and an epoxidized unsaturated ester composition andreacting the hydrogen sulfide and the epoxidized unsaturated ester toproduce the hydroxy thiol ester composition.

In some embodiments, the epoxidized unsaturated ester compositionincludes epoxidized unsaturated esters that have an average of at least1 ester groups and an average of at least 1 epoxide groups perepoxidized unsaturated ester molecule.

The process for producing or preparing the hydroxy thiol estercomposition can be applied to any of the epoxidized unsaturated estersdescribed herein and used to produce any hydroxy thiol ester describedherein. The process for producing the hydroxy thiol ester can alsoinclude any additional process steps or process conditions as describedherein. Additionally, the process for producing the hydroxy thiol estercan form any hydroxy thiol ester described herein.

In some embodiments, the epoxidized unsaturated ester composition is anepoxidized natural source oil. In some embodiments, the epoxidizedunsaturated ester composition is soybean oil. Other suitable types ofepoxidized unsaturated ester compositions, including the natural sourceoils described herein, will be apparent to those of skill in the art andare to be included within the scope of the present invention.

In some aspects, the hydroxy thiol ester is produced by contactinghydrogen sulfide with the epoxidized natural source oil under thereaction conditions to form the hydroxy thiol ester in the presence ofan optional catalyst. In some embodiments, the catalyst can be aheterogeneous catalyst or a homogeneous catalyst. Examples of suitablecatalysts are described herein. Additional types of suitable catalystswill be apparent to those of skill in the art and are to be consideredwithin the scope of the present invention.

In some aspects the reaction between the epoxidized unsaturated esteroccurs in the presence of a solvent. In other aspects the reactionbetween the epoxidized unsaturated ester and hydrogen sulfide occurs inthe substantial absence of a solvent. In aspects that include thepresence of a solvent, the solvent is selected from the groupsconsisting of an aliphatic hydrocarbon, an ether, an aromatic compound,and combinations thereof. Generally, the solvent, regardless of itschemical class, includes from 1 to 20 carbon atoms; or alternatively,from 3 to 10 carbon atoms. When the solvent includes the aliphatichydrocarbon, the aliphatic hydrocarbon is butane, isobutane, pentane,hexane, heptane, octane, or any mixture thereof. When the solventincludes the aromatic compound, the aromatic compound is benzene,toluene, xylene, ethylbenzene, or any mixture thereof. When the solventincludes the ether, the ether is diethyl ether, dipropyl ether,tetrahydrofuran, or any mixture thereof. Other suitable solvents will beapparent to those of skill in the art and are to be considered withinthe scope of the present invention.

When a solvent is used for the reaction between the hydrogen sulfide andthe epoxidized unsaturated ester, the quantity of solvent can be anyamount that facilitates the reaction. In some embodiments, the mass ofthe solvent is less than 30 times the mass of the epoxidized unsaturatedester. In other embodiments, the mass of the solvent is less than 20times the mass of the epoxidized unsaturated ester; alternatively, lessthan 15 times the mass of the epoxidized unsaturated ester;alternatively, less than 10 times the mass of the epoxidized unsaturatedester; or alternatively, less than 5 times the mass of the epoxidizedunsaturated ester. In other embodiments, the mass of the solvent is from2 times to 20 times the mass of the epoxidized unsaturated ester;alternatively, from 3 times to 15 times the mass of the epoxidizedunsaturated ester; alternatively; 4 times to 15 times the mass of theepoxidized unsaturated ester; or alternatively, from 5 times to 10 timesthe mass of the epoxidized unsaturated ester.

The hydrogen sulfide to molar equivalents of epoxide groups in theepoxidized unsaturated ester (hereinafter “hydrogen sulfide to epoxidegroup molar ratio”) utilized in the process to produce the hydroxy thiolester can be any hydrogen sulfide to epoxide group molar ratio thatproduces the desired hydroxy thiol ester. The molar equivalents ofepoxidized unsaturated ester epoxidized groups can be calculated by theequation:

$\frac{{EUES}\mspace{14mu}{Mass}}{{EUES}\mspace{14mu}{GMW}} \times {EUES}\mspace{14mu}{Epoxide}$In this equation, EUES GMW is the average gram molecular weight of theepoxidized unsaturated ester, EUES Mass is the mass of the epoxidizedunsaturated ester, and EUES Epoxide is the average number of epoxidegroups per epoxidized unsaturated ester molecule. In some embodiments,the hydrogen sulfide to epoxide group molar ratio is greater than 0.2.In other embodiments, the hydrogen sulfide to epoxide group molar ratiois greater than 0.5; alternatively, greater than 1; or alternatively,greater than 2. In other embodiments, the hydrogen sulfide to epoxidegroup molar ratio ranges from 0.2 to 5; alternatively, from 0.5 to 4; oralternatively, from 0.75 to 3. In some embodiments, the hydrogen sulfideto epoxide group molar ratio is greater than 2. In other embodiments,the hydrogen sulfide to epoxide group molar ratio is greater than 5;alternatively, greater than 10; alternatively, greater than 15; oralternatively, greater than 20. In other embodiments, the hydrogensulfide to epoxide group molar ratio can be from 0.2 to 500;alternatively, from 0.5 to 400; alternatively, from 1 to 300;alternatively, from 2 to 250; alternatively, 5 to 200; or alternatively,from 10 to 100.

The reaction of the epoxidized unsaturated ester and hydrogen sulfidecan occur in a batch reactor or a continuous reactor. Suitable types ofbatch and continuous reactors are described herein. Other suitable typesof batch and continuous reactors will be apparent to those of skill inthe art and are to be considered within the scope of the presentinvention.

The time required for the reaction of the epoxidized unsaturated esterand hydrogen sulfide can be any time required to form the describedhydroxy thiol ester. Generally, the time required for the reaction ofthe epoxidized unsaturated ester and hydrogen sulfide is at least 15minutes. In some embodiments, the time required for the reaction of theunsaturated ester and hydrogen sulfide ranges from 15 minutes to 72hours; alternatively, from 30 minutes to 48 hours; alternatively, from45 minutes to 36 hours.

In some embodiments, the hydroxy thiol ester composition includeshydroxy thiol ester molecules that have an average of greater than 2.5weight percent thiol sulfur. In some embodiments, the hydroxy thiolester composition includes hydroxy thiol ester molecules that have anaverage of greater than 5 weight percent thiol sulfur. Alternatively, insome embodiments, the hydroxy thiol ester molecules have an averageranging from 8 to 10 weight percent thiol sulfur.

In other aspects, the process producing the hydroxy thiol estercomposition includes producing hydroxy thiol ester molecules having anaverage of greater than 40 percent of the sulfide-containing ester totalside chains comprise a sulfide group. Additional embodiments wherein thehydroxy thiol ester comprises a percentage of sulfide-containing estertotal side chains are described herein.

In embodiments, the process to produce the hydroxy thiol ester furthercomprises a step to remove residual hydrogen sulfide after reacting thehydrogen sulfide and the epoxidized unsaturated ester composition. Insome embodiments, the hydroxy thiol ester is vacuum stripped. In someembodiments, the hydroxy thiol ester is vacuum stripped at a temperatureranging between 25° C. and 250° C.; or alternatively, between 50° C. and200° C. In other embodiments, the hydroxy thiol ester is sparged with aninert gas to remove hydrogen sulfide. In some embodiments, the hydroxythiol ester is sparged with an inert gas at a temperature between 25° C.and 250° C.; or alternatively, between 50° C. and 200° C. In someaspects, the inert gas is nitrogen. Generally, the stripped or spargedhydroxy thiol ester comprises less than 0.1 weight percent hydrogensulfide. In other embodiments, the stripped or sparged hydroxy thiolester comprises less than 0.05 weight percent hydrogen sulfide;alternatively, less than 0.025 weight percent hydrogen sulfide; oralternatively, less than 0.01 weight percent hydrogen sulfide.

The reaction between the hydrogen sulfide and the epoxidized unsaturatedester can be performed at any temperature capable of forming the hydroxythiol ester. In some embodiments, the epoxidized unsaturated ester andhydrogen sulfide can be reacted at a reaction temperature greater than−20° C. In other embodiments, the reaction temperature is greater than0° C.; alternatively, greater than 20° C.; alternatively, greater than50° C.; or alternatively, greater than 80° C. In yet other embodiments,the reaction temperature ranges from −20° C. to 200° C.; alternatively,from 20° C. to 170° C.; or alternatively, from 80° C. to 140° C.

The reaction between the epoxidized unsaturated ester and hydrogensulfide can be performed at any reaction pressure that maintains asubstantial portion of the hydrogen sulfide in a liquid state. In someembodiments, the reaction pressure ranges from 100 psig to 2000 psig. Inother embodiments, the reaction a pressure ranges from 150 to 1000 psig;or alternatively, from 200 to 600 psig.

In another aspect, the process to produce a hydroxy thiol ester producesa hydroxy thiol ester having an epoxide group to thiol group molar ratioless than 3.3. In another aspect, the process to produce a hydroxy thiolester produces a hydroxy thiol ester having an epoxide group to thiolgroup molar ratio less than 2. Other hydroxy thiol ester epoxide groupto thiol group molar ratios are described herein. Alternatively, thehydroxy thiol ester epoxide group to thiol group molar ratio can be lessthan 1.5; alternatively, less than 1.0; alternatively, less than 0.5;alternatively, less that 0.25; or alternatively, less than 0.1. In otherembodiments, the hydroxy thiol ester can be substantially free ofepoxide groups.

In another aspect, the process to produce hydroxy thiol ester produces ahydroxy thiol ester wherein at least 20 percent of the side chainscomprise an α-hydroxy thiol group. Other hydroxy thiol ester embodimentswherein the hydroxy thiol ester contains a percentage of side chainscomprising α-hydroxy thiol groups are described herein.

Hydroxy Thiol Ester from a Polyol and a Hydroxy Thiol ContainingCarboxylic Acid Derivative

As another embodiment of the present invention, another process toprepare the hydroxy thiol ester is advantageously provided. In thisembodiment, the process includes the steps of contacting a compositioncomprising a polyol with a composition comprising a hydroxy thiolcontaining carboxylic acid and/or thiol containing carboxylic acidderivative and reacting the polyol and hydroxy thiol containingcarboxylic acid and/or hydroxy thiol containing carboxylic acid to forma hydroxy thiol ester composition. This process can be applied to anypolyol, any hydroxy thiol containing carboxylic acid, or any thiolcontaining carboxylic acid derivative described herein. The process forproducing the hydroxy thiol ester composition can also include anyadditional process steps or process conditions described herein.Additionally, the process for producing the hydroxy thiol estercomposition can form any thiol ester described herein.

In some embodiments, the hydroxy thiol ester composition includeshydroxy thiol ester molecules that have an average of at least 1 estergroups per hydroxy thiol ester molecule and an average of at least 1α-hydroxy thiol groups per hydroxy thiol ester molecule.

The polyol used to produce the hydroxy thiol ester by contacting apolyol and a hydroxy thiol carboxylic acid and/or hydroxy thiolcarboxylic acid equivalent (for example a hydroxy thiol carboxylic acidmethyl ester) can be any polyol or mixture of polyols that can producethe described thiol containing ester.

In one aspect, the polyol used to produce the hydroxy thiol ester cancomprise from 2 to 20 carbon atoms. In other embodiments, the polyolcomprises from 2 to 10 carbon atoms; alternatively from 2 to 7 carbonatoms; alternatively from 2 to 5 carbon atoms. In further embodiments,the polyol may be a mixture of polyols having an average of 2 to 20carbon atoms; alternatively, an average of from 2 to 10 carbon atoms;alternatively, an average of 2 to 7 carbon atoms; alternatively anaverage of 2 to 5 carbon atoms.

In another aspect, the polyol used to produce the hydroxy thiol estercan have any number of hydroxy groups needed to produce the hydroxythiol ester as described herein. In some embodiments, the polyol has 2hydroxy groups; alternatively 3 hydroxy groups; alternatively, 4 hydroxygroups; alternatively, 5 hydroxy groups; or alternatively, 6 hydroxygroups. In other embodiments, the polyol comprises at least 2 hydroxygroups; alternatively at least 3 hydroxy groups; alternatively, at least4 hydroxy groups; or alternatively, at least 5 hydroxy groups; at least6 hydroxy groups. In yet other embodiments, the polyol comprises from 2to 8 hydroxy groups; alternatively, from 2 to 4 hydroxy groups; oralternatively from 4 to 8 hydroxy groups.

In further aspects, the polyol used to produce the hydroxy thiol esteris a mixture of polyols. In an embodiment, the mixture of polyols has anaverage of at least 1.5 hydroxy groups per polyol molecule. In otherembodiments, the mixture of polyols has an average of at least 2 hydroxygroups per polyol molecule; alternatively, an average of at least 2.5hydroxy groups per polyol molecule; alternatively, an average of atleast 3.0 hydroxy groups per polyol molecule; or alternatively, anaverage of at least 4 hydroxy groups per polyol molecule. In yet anotherembodiments, the mixture of polyols has an average of 1.5 to 8 hydroxygroups per polyol molecule; alternatively, an average of 2 to 6 hydroxygroups per polyol molecule; alternatively, an average of 2.5 to 5hydroxy groups per polyol molecule; alternatively, an average of 3 to 4hydroxy groups per polyol molecule; alternatively, an average of 2.5 to3.5 hydroxy groups per polyol molecule; or alternatively, an average of2.5 to 4.5 hydroxy groups per polyol molecule.

In yet another aspect, the polyol or mixture of polyols used to producethe hydroxy thiol ester has a molecular weight or average molecularweight less than 500. In other embodiments, the polyol or mixture ofpolyols have a molecular weight or average molecular weight less than300; alternatively less than 200; alternatively, less than 150; oralternatively, less than 100.

The hydroxy thiol carboxylic acid and/or hydroxy thiol carboxylic acidequivalent used to produce the hydroxy thiol ester by contacting apolyol and a hydroxy thiol carboxylic acid and/or hydroxy thiolcarboxylic acid equivalent can be any hydroxy thiol carboxylic acidmixture comprising hydroxy thiol carboxylic acids, hydroxy thiolcarboxylic acid equivalent or mixture comprising hydroxy thiolcarboxylic acid equivalents that can produce the described hydroxy thiolcontaining ester. When talking about the characteristics hydroxy thiolcarboxylic acid equivalent or hydroxy thiol carboxylic acid equivalents,properties such as number of carbon atoms, average number of carbonatom, molecular weight or average molecular weight, number of thiolgroup, and average number of thiol groups, one will understand the theseproperties will apply to the portion of the thiol carboxylic acidequivalent which adds to the polyol to form the thiol ester.

In an aspect, the hydroxy thiol carboxylic acid and/or hydroxy thiolcarboxylic acid equivalent used to produce the thiol ester comprisesfrom 2 to 28 carbon atoms. In an embodiment, the hydroxy thiolcarboxylic acid and/or hydroxy thiol carboxylic acid equivalentscomprises from 4 to 26 carbon atoms; alternatively, from 8 to 24 carbonatoms; alternatively, from 12 to 24 carbon atoms; or alternatively, from14 to 20 carbon atoms. In other embodiments, a mixture comprisinghydroxy thiol carboxylic acids and/or mixture comprising hydroxy thiolcarboxylic acid equivalents has an average of 2 to 28 carbon atoms percarboxylic acid and/or carboxylic acid equivalent; alternatively, from 4to 26 carbon per carboxylic acid and/or carboxylic acid equivalent;alternatively, from 8 to 24 carbon atoms per carboxylic acid and/orcarboxylic acid equivalent; alternatively, from 12 to 24 carbon atomsper carboxylic acid and/or carboxylic acid equivalent; or alternatively,from 14 to 20 carbon atoms per carboxylic acid and/or carboxylic acidequivalent.

In another aspect, the hydroxy thiol carboxylic acid and/or hydroxythiol carboxylic acid equivalent used to produce the thiol ester has atleast 1 thiol group; alternatively 2 thiol groups. In some embodiments,a mixture comprising hydroxy thiol carboxylic acids and/or mixturecomprising hydroxy thiol carboxylic acid equivalents has an average offrom 0.5 to 3 thiol groups per carboxylic acid and/or carboxylic acidequivalent; alternatively, an average of from 1 to 2 thiol groups percarboxylic acid and/or carboxylic acid equivalent.

In another aspect, the hydroxy thiol carboxylic acid and/or hydroxythiol carboxylic acid equivalent used to produce the thiol ester has atleast 1 hydroxy group; alternatively, at least 2 hydroxy groups. In someembodiments, a mixture comprising hydroxy thiol carboxylic acids and/ormixture comprising hydroxy thiol carboxylic acid equivalents has anaverage of from 0.5 to 3 hydroxy groups per carboxylic acid and/orcarboxylic acid equivalent; alternatively, an average of from 1 to 2hydroxy groups per carboxylic acid and/or carboxylic acid equivalent.

In another aspect, the hydroxy thiol carboxylic acid and/or hydroxythiol carboxylic acid equivalent used to produce the hydroxy thiol esterhas a molecular weight greater than 100; alternatively greater than 180;alternatively greater than 240; or alternatively greater than 260. Inother embodiments, the hydroxy thiol carboxylic acid and/or hydroxythiol carboxylic acid equivalent has a molecular weight from 100 to 500;alternatively, from 120 to 420; alternatively, from 180 to 420;alternatively, from 240 to 420; a mixture or alternatively, from 260 to360. In some embodiments, a mixture comprising hydroxy thiol carboxylicacids and/or mixture comprising hydroxy thiol carboxylic acidequivalents has an average molecular weight greater than 100 percarboxylic acid and/or carboxylic acid equivalent; alternatively greaterthan 180 per carboxylic acid and/or carboxylic acid equivalent;alternatively greater than 240 per carboxylic acid and/or carboxylicacid equivalent; or alternatively greater than 260 per carboxylic acidand/or carboxylic acid equivalent. In yet other embodiments, the mixturecomprising hydroxy thiol carboxylic acid and/or mixture comprisinghydroxy thiol carboxylic acid equivalents has an average molecularweight from 100 to 500 per carboxylic acid and/or carboxylic acidequivalent; alternatively, from 120 to 420 per carboxylic acid and/orcarboxylic acid equivalent; alternatively, from 180 to 420 percarboxylic acid and/or carboxylic acid equivalent; alternatively, from240 to 420 per carboxylic acid and/or carboxylic acid equivalent; amixture or alternatively, from 260 to 360 per carboxylic acid and/orcarboxylic acid equivalent.

In some aspects, the reaction between the polyol and the hydroxy thiolcontaining carboxylic acid and/or hydroxy thiol containing carboxylicacid derivative occurs in the presence of a solvent. In other aspects,the reaction between the polyol and the hydroxy thiol containingcarboxylic acid and/or hydroxy thiol containing carboxylic acidderivative occurs in the substantial absence of a solvent. In aspectswherein the reaction between the polyol and the hydroxy thiol containingcarboxylic acid and/or hydroxy thiol containing carboxylic acidderivative occurs in the presence of a solvent, the solvent is selectedfrom the group consisting of an aliphatic hydrocarbon, an ether, anaromatic compound, or any combination thereof. Generally, the solvent,regardless of its chemical class, includes from 1 to 20 carbon atoms;alternatively, from 3 to 10 carbon atoms. When the solvent includes thealiphatic hydrocarbon, the aliphatic hydrocarbon is butane, isobutane,pentane, hexane, heptane, octane, or any mixture thereof. When thesolvent includes the aromatic compound, the aromatic compound isbenzene, toluene, xylene, ethylbenzene, or any mixture thereof. When thesolvent includes the ether, the ether is diethyl ether, dipropyl ether,tetrahydrofuran, and any mixture thereof.

When a solvent is used for the reaction between the polyol and thehydroxy thiol containing carboxylic acid and/or hydroxy thiol containingcarboxylic acid derivative, the quantity of solvent can be any amountthat facilitates the reaction. In some embodiments, the mass of thesolvent is less than 30 times the mass of the hydroxy thiol containingcarboxylic acid and/or hydroxy thiol containing carboxylic acidderivative. In other embodiments, the mass of the solvent is less than20 times the mass of the hydroxy thiol ester; alternatively, less than15 times the mass of the hydroxy thiol containing carboxylic acid and/orhydroxy thiol containing carboxylic acid derivative; alternatively, lessthan 10 times the mass of the hydroxy thiol containing carboxylic acidand/or hydroxy thiol containing carboxylic acid derivative; oralternatively, less than 5 times the mass of the hydroxy thiolcontaining carboxylic acid and/or hydroxy thiol containing carboxylicacid derivative. In other embodiments, the mass of the solvent is from 2times to 20 times the mass of the hydroxy thiol containing carboxylicacid and/or hydroxy thiol containing carboxylic acid derivative;alternatively, from 3 times to 15 times the mass of the hydroxy thiolcontaining carboxylic acid and/or hydroxy thiol containing carboxylicacid derivative; or alternatively, from 5 times to 10 times the mass ofthe hydroxy thiol containing carboxylic acid and/or hydroxy thiolcontaining carboxylic acid derivative.

The equivalents of hydroxy thiol containing carboxylic acid derivativeand/or hydroxy thiol containing carboxylic acid derivative carboxylicacid groups to equivalents of polyol hydroxy groups molar ratio(hereinafter referred to as “carboxylic acid group to polyol hydroxygroup molar ratio”) utilized in the process to produce the hydroxy thiolester can be any carboxylic acid group to polyol hydroxy group molarratio that produces the desired hydroxy thiol ester. In someembodiments, the carboxylic acid group to polyol hydroxy group molarratio is greater than 0.4. In other embodiments, the carboxylic acidgroup to polyol hydroxy group molar ratio is greater than 0.6;alternatively, greater than 0.8; alternatively, greater than 1; oralternatively, greater than 1.1. In other embodiments, the carboxylicacid group to polyol hydroxy group molar ratio ranges from 0.4 to 1.3;alternatively, from 0.6 to 1.2, or alternatively, from 0.8 to 1.1.

In some aspects, the reaction between the polyol and the hydroxy thiolcontaining carboxylic acid and/or hydroxy thiol containing carboxylicacid derivative is catalyzed. In some embodiments, the catalyst is amineral acid, such as sulfuric or phosphoric acid. In other embodiments,the catalyst is an organic acid. In embodiments, for example, theorganic acid is methane sulfonic acid or toluene sulfonic acid. Othersuitable types of catalyst will be apparent to those of skill in the artand are to be considered within the scope of the present invention.

The reaction of the polyol and the hydroxy thiol containing carboxylicacid and/or hydroxy thiol containing carboxylic acid derivative canoccur in a batch reactor or a continuous reactor, as described herein.The reaction between the polyol and the hydroxy thiol containingcarboxylic acid and/or hydroxy thiol containing carboxylic acidderivative can be performed at any temperature capable of forming thehydroxy thiol ester. In some embodiments, the polyol and the hydroxythiol containing carboxylic acid and/or hydroxy thiol containingcarboxylic acid derivative can be reacted at a temperature greater than20° C. In other embodiments, the polyol and the hydroxy thiol containingcarboxylic acid and/or hydroxy thiol containing carboxylic acidderivative can be reacted at a temperature greater than 50° C.;alternatively, greater than 75° C.; or alternatively, greater than 100°C. In yet other embodiments, the polyol and the hydroxy thiol containingcarboxylic acid and/or hydroxy thiol containing carboxylic acidderivative can be reacted at a temperature from 20° C. to 250° C.;alternatively, from 50° C. to 200° C.; alternatively, from 75° C. to175° C.; or alternatively, from 100° C. to 150°.

The time required for the reaction of the polyol and the hydroxy thiolcontaining carboxylic acid and/or hydroxy thiol containing carboxylicacid derivative can be any time required to form the described hydroxythiol ester composition. Generally, the reaction time is at least 5minutes. In some embodiments, the reaction time is at least 30 minutes;alternatively, at least 1 hour; or alternatively, at least 2 hours. Inyet other embodiments, the reaction time ranges from 5 minutes to 72hours; alternatively, from 30 minutes to 48 hours; alternatively, from 1hour minutes to 36 hours; or alternatively, from 2 hours and 24 hours.

The reaction between the polyol and the hydroxy thiol containingcarboxylic acid and/or hydroxy thiol containing carboxylic acidderivative can be performed at any reaction pressure that maintains thepolyol and the hydroxy thiol containing carboxylic acid and/or hydroxythiol containing carboxylic acid derivative in a liquid state. In someembodiments, the reaction pressure ranges from 0 psia to 2000 psia. Inother embodiments, the reaction pressure ranges from 0 psia to 1000psia; alternatively, from 0 psia and 500 psia; or alternatively, from 0psia to 300 psia.

In some embodiments, the process to produce the hydroxy thiol estercomposition by reacting a polyol and the hydroxy thiol containingcarboxylic acid and/or hydroxy thiol containing carboxylic acidderivative can further include a step to remove excess or residualpolyol, hydroxy thiol containing carboxylic acid, and/or hydroxy thiolcontaining carboxylic acid derivative once the polyol has reacted withthe hydroxy thiol containing carboxylic acid or hydroxy thiol containingcarboxylic acid derivative. In some embodiments, the thiol ester isvacuum stripped. In some embodiments, the hydroxy thiol ester is vacuumstripped at a temperature between 25° C. and 250° C.; or alternatively,between 50° C. and 200° C. In other embodiments, the hydroxy thiol esteris sparged with an inert gas to remove excess polyol, hydroxy thiolcontaining carboxylic acid, and/or hydroxy thiol containing carboxylicacid derivative. In some embodiments, the hydroxy thiol ester is spargedwith an inert gas at a temperature between 25° C. and 250° C., oralternatively, between 50° C. and 200° C. In some aspects, the inert gasis nitrogen. Generally, the stripped or sparged hydroxy thiol ester oilcomprises less than 5 excess polyol, hydroxy thiol containing carboxylicacid, or hydroxy thiol containing carboxylic acid derivative. In otherembodiments, the stripped or sparged hydroxy thiol ester oil comprisesless than 2 weight percent excess polyol, hydroxy thiol containingcarboxylic acid, and/or hydroxy thiol containing carboxylic acidderivative; less than 1 weight percent excess polyol, hydroxy thiolcontaining carboxylic acid, and/or hydroxy thiol containing carboxylicacid derivative; or alternatively, less than 0.5 weight percent excesspolyol, hydroxy thiol containing carboxylic acid, and/or hydroxy thiolcontaining carboxylic acid derivative.

Method of Making Thioacrylate Esters

A method of making a thioacrylate containing ester composition isadvantageously provided as another embodiment of the present invention.The process for producing the thioacrylate containing ester comprisingcontacting a thiol ester with an acrylate and converting at least onethiol group to a thiol acrylate group. The process can be applied to anyof the thiol esters described herein and used to any thioacrylate esterdescribed herein. The process for producing the thioacrylate ester canalso include any additional process steps or process conditionsdescribed herein.

The acrylate compound can be any acrylate compound capable of reactingwith a thiol group to form the thiol acrylate group. In someembodiments, the acrylate compound can be an acrylic halide. In otherembodiments, the acrylate compound can be an acrylic acid. In yet otherembodiments, the acrylate compound can be an acrylic anhydride.

In some embodiments of the present invention, the acrylate compositionhas the following structure:

In the acrylate composition structure, Y is selected from the groupconsisting of hydrogen, a halogen, and OR⁴; and R⁷, R⁸, and R⁹ areindependently selected from the group consisting of hydrogen, C₁ to C₂₀organyl groups, and C₁ to C₂₀ hydrocarbyl groups. In furtherembodiments, R⁷, R⁸, and R⁹ are selected from hydrogen, C₁ to C₁₀organyl groups, and C₁ to C₁₀ hydrocarbyl groups; or alternatively,selected from C₁ to C₅ organyl groups, and C₁ to C₅ hydrocarbyl groups.In certain embodiments, R⁷, R⁸, and R⁹ are independently selected fromthe group consisting of hydrogen and a methyl group. In some specificembodiments, R⁸ and R⁹ are hydrogen and R⁷ is selected from hydrogen, amethyl group or a mixture thereof; alternatively, R⁸ and R⁹ are hydrogenand R⁷ is a methyl group; or alternatively, R⁷, R⁸, and R⁹ are hydrogen.In some embodiments, R⁴ is independently selected from the groupconsisting of C₁ to C₂₀ organyl groups, and C₁ to C₂₀ hydrocarbylgroups; alternatively, from C₁ to C₁₀ organyl groups, and C₁ to C₁₀hydrocarbyl groups; or alternatively, selected from C₁ to C₅ organylgroups, and C₁ to C₅ hydrocarbyl groups.

In other embodiments, the acrylate compound can be an acrylic anhydridehaving the structure:

In this acrylic anhydride structure, Y is selected from the groupconsisting of hydrogen, a halogen, and OR⁴; and R⁷, R⁸, and R⁹ areindependently selected from the group consisting of hydrogen, C₁ to C₂₀organyl groups, and C₁ to C₂₀ hydrocarbyl groups. In furtherembodiments, R⁷, R⁸, and R⁹ are selected from hydrogen, C₁ to C₁₀organyl groups, and C₁ to C₁₀ hydrocarbyl groups; or alternatively,selected from C₁ to C₅ organyl groups, and C₁ to C₅ hydrocarbyl groups.In certain embodiments, R⁷, R⁸, and R⁹ are independently selected fromthe group consisting of hydrogen and a methyl group. In some specificembodiments, R⁸ and R⁹ are hydrogen and R⁷ is selected from hydrogen, amethyl group or a mixture thereof; alternatively, R⁸ and R⁹ are hydrogenand R⁷ is a methyl group; or alternatively, R⁷, R⁸, and R⁹ can behydrogen. In some embodiments, R₄ is independently selected from thegroup consisting of C₁ to C₂₀ organyl groups, and C₁ to C₂₀ hydrocarbylgroups; alternatively, from C₁ to C₁₀ organyl groups, and C₁ to C₁₀hydrocarbyl groups; or alternatively, selected from C₁ to C₅ organylgroups, and C₁ to C₅ hydrocarbyl groups.

In some embodiments of the present invention, the Y within the acrylatecomposition can be a halide. For example, the halide can be chlorine,bromine and iodine. The acrylate composition can include acryloylchloride, methacryloyl chloride and mixtures thereof. The acrylicanhydrides compounds can include acrylic anhydride, methacrylicanhydride, or mixtures thereof.

In some aspects, the conversion of the thiol group to a thioacrylategroup occurs in the presence of a solvent. In other aspects theconversion of the thiol group to a thioacrylate group occurs in thesubstantial absence of a solvent. In aspects wherein the conversion ofthe thiol group to a thioacrylate group occurs in the presence of asolvent, the solvent may be an aliphatic hydrocarbon, an ether, andaromatic compound. Generally, the solvent, regardless of its chemicalclass, includes from 1 to 20 carbon atoms; or alternatively, from 3 to10 carbon atoms. When the solvent includes the aliphatic hydrocarbon,the aliphatic hydrocarbon is butane, isobutane, pentane, hexane,heptane, octane, or any mixture thereof. When the solvent includes thearomatic compound, the aromatic compound is benzene, toluene, xylene,ethylbenzene, or any mixture thereof. When the solvent includes theether, the ether is diethyl ether, dipropyl ether, tetrahydrofuran, orany mixture thereof.

When a solvent is used for the conversion of the thiol group to athioacrylate group, the quantity of solvent can be any amount thatfacilitates the reaction. In some embodiments, the mass of the solventis less than 30 times the mass of the thiol ester. In other embodiments,the mass of the solvent is less than 20 times the mass of the thiolester; alternatively, less than 15 times the mass of the thiol ester;alternatively, less than 10 times the mass of the thiol ester; oralternatively, less than 5 times the mass of the thiol ester. In otherembodiments, the mass of the solvent is from 2 times to 20 times themass of the thiol ester; alternatively, from 3 times to 15 times themass of the thiol ester; alternatively, 4 times to 15 times the mass ofthe thiol ester; or alternatively, from 5 times to 10 times the mass ofthe thiol ester.

In some aspects the conversion of the thiol group to the thioacrylategroup occurs in the presence of a catalyst. In some embodiments, thecatalyst is homogeneous. In some embodiments, the catalyst is an organicamine. Examples of suitable organic amines include triethylamine,tripropylamine, tributylamine, and pyridine. In other embodiments, thecatalyst is heterogeneous. Examples of suitable catalysts includeAmberlyst A-21 and Amberlyst A-26. Other suitable catalysts will beapparent to those of skill in the art and are to be considered withinthe scope of the present invention.

The conversion of the thiol group to a thioacrylate group can beperformed at any conversion temperature that is capable of convertingthe thiol group to a thioacrylate group. In some embodiments, theconversion temperature is greater than −20° C. In other embodiments, theconversion temperature is greater than 0° C.; alternatively, greaterthan 20° C.; alternatively, greater than 50° C.; alternatively, greaterthan 80° C.; or alternatively, greater than 100° C. In yet otherembodiments, the conversion temperature ranges from −20° C. to 250° C.;alternatively, from 20° C. to 200° C.; or alternatively, from 50° C. to150° C.

The conversion time required for the conversion of the thiol group to athioacrylate group can be any time required to form the describedthioacrylate containing ester. Generally, the conversion time is atleast 5 minutes. In some embodiments, the conversion time is at least 15minutes; alternatively, at least 30 minutes; alternatively, at least 45minutes; or alternatively, at least 1 hour. In other embodiments, theconversion time ranges from 15 minutes to 12 hours; alternatively, from30 minutes to 6 hours; or alternatively, from 45 minutes to 3 hours.

The conversion of the thiol group to a thioacrylate group can beperformed at any conversion pressure that maintains the thiol ester andthe acrylate compound in the liquid state. In some embodiments, theconversion pressure ranges from 0 psia to 2000 psia. In otherembodiments, the conversion pressure ranges from 0 psia to 1000 psia; oralternatively, from 0 psia to 500 psia.

Process for Producing Cross-Linked Thiol Ester

As an embodiment of the present invention, a process for producing across-linked thiol ester composition is advantageously provided.Minimally, in some embodiments, the process to produce the cross-linkedthiol ester composition comprises contacting a thiol ester compositionwith an oxidizing agent and reacting the thiol ester composition and anoxidizing agent to form the thiol ester oligomer having at least twothiol ester monomers connected by a polysulfide linkage having thestructure —S_(Q)—, wherein Q is an integer greater than 1. The disclosedmethod may be applied to any thiol ester described herein to produce anycross-linked thiol ester composition as described herein. The process toproduce the cross-linked thiol ester composition can also include anyadditional process steps or process conditions as described herein.

In an aspect, the oxidizing agent can be elemental sulfur, oxygen, orhydrogen peroxide. In some embodiments, the oxidizing agent can beelemental sulfur. In other embodiments, the oxidizing agent can beoxygen. In some oxygen oxidizing agent embodiments, the oxidizing agentis air. In further embodiments, the oxidizing agent is hydrogenperoxide.

When elemental sulfur is used as the oxidizing agent, the quantity ofelemental sulfur utilized to form the cross-linked thiol estercomposition is determined as a function of the thiol sulfur content ofthe thiol ester composition. In an aspect, the weight ratio of elementalsulfur to thiol sulfur in the thiol ester composition is at least 0.5.In some embodiments, the weight ratio of elemental sulfur to thiolsulfur in the thiol ester composition is at least 5; alternatively, atleast 10, alternatively, at least 15, or alternatively, at least 20. Inother embodiments, the weight ratio of elemental sulfur to thiol sulfurin the thiol ester composition ranges from 0.5 to 32; alternatively,ranges from 1 to 24; alternatively, ranges from 2 to 16; oralternatively, ranges from 3 to 10.

In an aspect, the reaction of the thiol ester and elemental sulfuroccurs in the presence of a catalyst. The catalyst can be any catalystthat catalyzes the formation of the polysulfide linkage between at leasttwo thiol ester monomers. In some embodiments, the catalyst is an amine.In further embodiments, the catalyst is a tertiary amine.

The formation of the cross-linked thiol ester can occur in a batchreactor or a continuous reactor, as described herein. The formation ofthe cross-linked thiol ester can occur at any temperature capable offorming the thiol ester. In some embodiments, the formation of thecross-linked thiol ester can occurs at a temperature greater than 25° C.In other embodiments, the formation of the cross-linked thiol ester canoccurs at a temperature greater than 50° C.; alternatively, greater than70° C.; or alternatively, greater than 80° C. In yet other embodiments,the formation of the cross-linked thiol ester occurs at a temperaturefrom 25° C. to 150° C.; alternatively, from 50° C. to 150° C.;alternatively, from 70° C. to 120° C.; or alternatively, from 80° C. to110° C.

The time required to form the cross-linked thiol ester can be any timerequired to form the desired cross-linked thiol ester. Generally, thetime required to form the cross-linked thiol ester is at least 15minutes. In some embodiments, the time required to form the cross-linkedthiol ester is at least 30 minutes; alternatively, at least 1 hour; oralternatively, at least 2 hours. In yet other embodiments, the timerequired to form the cross-linked thiol ester ranges from 15 minutes to72 hours; alternatively, from 30 minutes to 48 hours; alternatively,from 1 hour minutes to 36 hours; or alternatively, from 2 hours and 24hours.

In embodiments, the process to produce the cross-linked thiol esterfurther comprises a step to remove residual hydrogen sulfide. In someembodiments the cross-linked thiol ester is vacuum stripped. In someembodiments, the cross-linked thiol ester is vacuum striped at atemperature between 25° C. and 250° C.; alternatively, between 50° C.and 200° C.; or alternatively, 75 and 150° C. In some embodiments, thecross-linked thiol ester oil is sparged with an inert gas to removeresidual hydrogen sulfide. In other embodiments, the cross-linked thiolester is sparged with an inert gas at a temperature between 25° C. and250° C.; alternatively, between 50° C. and 200° C.; or alternatively,between 75 and 150° C. In yet other embodiments, the vacuum stripping isperformed while sparging the cross-linked thiol ester with an inert gas.In yet other embodiments, the vacuum stripping is performed whilesparging the cross-linked thiol ester an inert gas at a temperaturebetween 25° C. and 250° C.; alternatively, between 50° C. and 200° C.;or alternatively, 75 and 150° C. In some embodiments, the inert gas isnitrogen.

Generally, the stripped or sparged cross-linked thiol ester comprisesless than 0.1 weight percent hydrogen sulfide. In other embodiments, thestripped or sparged thiol-containing ester oil comprises less than 0.05weight percent hydrogen sulfide; alternatively, less than 0.025 weightpercent hydrogen sulfide; or alternatively, less than 0.01 weightpercent hydrogen sulfide.

Process for Preparing Sulfide-Containing Ester Composition

The present invention advantageously provides processes for producingsulfide-containing esters as embodiments of the present invention.Generally, the sulfide-containing esters can be prepared by twoprocesses. As an embodiment of the present invention, the first processused to produce a sulfide-containing ester comprises contacting anunsaturated ester and a mercaptan and reacting the unsaturated ester andmercaptan to form a sulfide-containing ester. As another embodiment ofthe present invention, the second process used to produce asulfide-containing ester comprises contacting an epoxidized unsaturatedester and a mercaptan sulfide and reacting the unsaturated ester andmercaptan to form a sulfide-containing ester. Additional aspects of thetwo sulfide-containing ester production processes are described below.

Sulfide-Containing Esters from Unsaturated Esters

The sulfide-containing esters and sulfide-containing ester compositionsdescribed herein can be produced by a process comprising contacting amercaptan and an unsaturated ester and reacting the mercaptan and theunsaturated ester to form a sulfide-containing ester. The process can beapplied to any of the unsaturated esters and mercaptans describedherein. The process for producing the sulfide-containing ester can alsoinclude any additional process steps or process conditions describedherein. Additionally, the process for producing the sulfide-containingester can form any sulfide-containing ester described herein.

In some aspects, the reaction between the mercaptan and the unsaturatedester occurs in the presence of a solvent. In other aspects the reactionbetween the mercaptan and the unsaturated ester occurs in thesubstantial absence of a solvent. When the reaction occurs in thepresence of a solvent, the solvent is selected from an aliphatichydrocarbon, an ether, an aromatic compound, an alcohol, or anycombination thereof. Generally, the solvent, regardless of its chemicalclass, can comprise from 1 to 20 carbon atoms; alternatively, from 3 to10 carbon atoms. When the solvent includes an aliphatic hydrocarbon, thealiphatic hydrocarbon is butane, isobutane, pentane, hexane, heptane,octane, or any mixture thereof. When the solvent includes an aromaticcompound, the aromatic compound is benzene, toluene, xylene,ethylbenzene, or any mixture thereof. When the solvent includes analcohol, the alcohol is methanol, 1-propanol, 2-propanol, 1-butanol,2-butanol, 2-methyl-2-proanol, or any mixture thereof. When the solventincludes an ether, the ether is diethyl ether, dipropyl ether,tetrahydrofuran, or any mixture thereof.

When a solvent is used for the reaction between the mercaptan and theunsaturated ester, the quantity of solvent can be any amount thatfacilitates the reaction, as understood by those of skill in the art. Insome embodiments, the mass of the solvent is less than 30 times the massof the unsaturated ester. In other embodiments, the mass of the solventis less than 20 times the mass of the unsaturated ester; alternatively,less than 15 times the mass of the unsaturated ester; alternatively,less than 10 times the mass of the unsaturated ester; or alternatively,less than 5 times the mass of the unsaturated ester. In otherembodiments, the mass of the solvent is from 2 times to 20 times themass of the unsaturated ester; alternatively, from 3 times to 15 timesthe mass of the unsaturated ester; alternatively, from 4 times to 15times the mass of the unsaturated ester; or alternatively, from 5 timesto 10 times the mass of the unsaturated ester.

The molar ratio of mercaptan to molar equivalents of unsaturated estercarbon-carbon double bonds (herein after “mercaptan to carbon-carbondouble bond molar ratio”) utilized in the process to produce thesulfide-containing ester can be any mercaptan to carbon-carbon doublebond molar ratio that produces the desired sulfide-containing ester. Themolar equivalents of unsaturated ester carbon-carbon double bonds iscalculated by the equation:

${\frac{{UES}\mspace{14mu}{Mass}}{{UES}\mspace{14mu}{GMW}} \times {UES}\mspace{14mu} C} = C$In this equation, UES GMW is the average gram molecular weight of theunsaturated ester, UES Mass is the mass of the unsaturated ester, andUES C═C is the average number of double bonds per unsaturated estermolecule. In some embodiments, the mercaptan to carbon-carbon doublebond molar ratio is greater than 0.25. In other embodiments, themercaptan to carbon-carbon double bond molar ratio is greater than 0.5;alternatively, greater than 0.75; alternatively, greater than 1;alternatively, greater than 1.25; or alternatively, greater than 1.5. Inother embodiments, the mercaptan to carbon-carbon double bond molarratio can range from 0.25 to 2; alternatively, from 0.5 to 1.5, oralternatively, from 0.75 to 1.25.

In some aspects the reaction between the mercaptan and the unsaturatedester is catalyzed. The reaction of the mercaptan and the unsaturatedester can be catalyzed by a heterogeneous catalyst or homogeneouscatalyst, as described herein. In some aspects, the reaction between themercaptan and the unsaturated ester is initiated by a free radicalinitiator or ultraviolet radiation, as described herein.

When the heterogeneous catalyst is used, the heterogeneous acid catalystis selected from the group consisting of acid clays, zeolites,cobalt/molybdenum oxide supported catalysts, and nickel/molybdenumsupported oxide catalysts. Examples of suitable catalysts are describedherein.

The free radical initiator can be any free radical initiator capable offorming free radicals under thermal or light photolysis. Generally, thefree radical initiator is selected from the general class of compoundshaving a —N═N— group or a —O—O— group. Specific classes of free radicalinitiators include diazo compounds, dialkyl peroxides, hydroperoxides,and peroxy esters. Specific initiators include azobenzene,2,2′-azobis(2-methylpropionitrile, 4,4′-azobis(4-cyanovaleric acid),1,1′-azobis(cyclohexanecarbo-nitrile), 2,2′-azobis(2methylpropane),2,2′-azobis(2-methylpropionamidine) dihydro-chloride,methylpropionitrile, azodicarboxamide, tert-butyl hydroperoxide,di-tert-butyl peroxide, octylperbenzoate. In some embodiments, the freeradical initiated reaction of the mercaptan and the unsaturated ester isperformed at a reaction temperature within ±50° C. of the 1 hour halflife of the free radical initiator. In other embodiments, the reactiontemperature is within ±25° C. of the 1 hour half life of the freeradical initiator; alternatively, the reaction temperature is within±20° C. of the 1 hour half life of the free radical initiator;alternatively, the reaction temperature is within ±15° C. of the 1 hourhalf life of the free radical initiator; or alternatively, the reactiontemperature is within ±10° C. of the 1 hour half life of the freeradical initiator. In embodiments where the free radical initiatedreaction of the mercaptan and the unsaturated ester is initiated bylight photolysis, the light can be any light capable creating freeradicals. In some embodiments, the light is UV radiation. Other sourcesof light capable of creating free radicals will be apparent to those ofskill in the art and are to be considered within the scope of thepresent invention.

In another aspect, the reaction of the mercaptan and the unsaturatedester is initiated by UV radiation. In these embodiments, the UVradiation may be any UV radiation capable of initiating the reaction ofthe mercaptan and the unsaturated ester. In some embodiments, the UVradiation is generated by a medium pressure mercury lamp.

The reaction of the mercaptan and the unsaturated ester can occur in abatch reactor of a continuous reactor. Any of the batch or continuousreactors described herein can be used in this reaction. Other suitablereactors will be apparent to those of skill in the art and are to beconsidered within the scope of the present invention.

The reaction time for reacting the mercaptan and the unsaturated estercan be any time required to form the sulfide-containing ester.Generally, the reaction time is at least 5 minutes. In some embodiments,the reaction time ranges from 5 minutes to 72 hours; alternatively, from10 minutes to 48 hours; or alternatively, from 15 minutes to 36 hours.

In some embodiments, the process to produce the sulfide-containing esterfurther comprises a step to remove any residual mercaptan that remainsafter reacting the mercaptan and the unsaturated ester. In someembodiments, the sulfide-containing ester is vacuum stripped to removethe residual mercaptan. In some embodiments, the sulfide-containingester is vacuum stripped at a temperature between 25° C. and 250° C.; oralternatively, between 50° C. and 200° C. In other embodiments, thesulfide-containing ester is sparged with an inert gas to remove theresidual mercaptan. In some embodiments, the sulfide-containing ester issparged with an inert gas at a temperature between 25° C. and 250° C.;or alternatively, between 50° C. and 200° C. In some aspects, the inertgas is nitrogen. Generally, the stripped or sparged sulfide-containingester comprises less than 5 weight percent of the mercaptan. In otherembodiments, the stripped or sparged sulfide-containing ester comprisesless than 2 weight percent of the mercaptan; alternatively, less than 1weight percent of the mercaptan; or alternatively, less than 0.5 weightpercent of the mercaptan.

The reaction between the mercaptan and the unsaturated ester can beperformed at any temperature capable of forming the sulfide-containingester. In some embodiments, the mercaptan and the unsaturated ester canbe reacted at a reaction temperature of greater than −20° C. In otherembodiments, the reaction temperature is greater than 0° C.;alternatively, greater than 20° C.; alternatively, greater than 50° C.;alternatively, greater than 80° C.; or alternatively, greater than 100°C. In yet other embodiments, the mercaptan and the unsaturated ester canbe reacted at a temperature from −20° C. to 250° C.; alternatively, from20° C. to 200° C.; or alternatively, from 80° C. to 160° C.

The reaction between the mercaptan and the unsaturated ester can beperformed at any pressure that maintains the mercaptan and theunsaturated ester in a substantially liquid state. In some embodiments,the mercaptan and the unsaturated ester can be performed at a reactionpressure ranging from 0 psig to 2000 psig. In other embodiments, thereaction pressure ranges from 0 psig to 1000 psig; alternatively, from 0psig to 500 psig; or alternatively, from 0 psig to 200 psig.

Using the disclosed process, sulfide-containing ester having a lowcarbon-carbon double bond to sulfide group molar ratio can be produced.In an aspect, the process for producing the sulfide-containing esterforms a sulfide-containing ester having a carbon-carbon double bond tothiol group molar ratio of less than 1.5. Additional carbon-carbondouble bond to sulfide group molar ratios are disclosed herein.

In other aspects, the process producing the sulfide-containing esterincludes producing sulfide-containing ester molecules having an averageof at least 40 percent of the sulfide-containing ester side chainscomprise a sulfide group. Additional embodiments wherein thesulfide-containing ester comprises a percentage of sulfide-containingester side chains are described herein.

Sulfide-Containing Esters from Epoxidized Unsaturated Esters

As another embodiment of the present invention, another process forproducing a class of sulfide-containing esters, which includes hydroxysulfide-containing esters, is advantageously provided. In thisembodiment, the hydroxy sulfide-containing esters and hydroxysulfide-containing ester compositions can be produced by a processcomprising the steps of contacting a mercaptan and an epoxidizedunsaturated ester and reacting the mercaptan and the epoxidizedunsaturated ester to produce or form the hydroxy sulfide-containingester. The process can be applied to any mercaptan and/or any epoxidizedunsaturated esters described herein. The process for producing thehydroxy sulfide-containing ester can also include any additional processsteps or process conditions as described herein. Additionally, theprocess for producing the hydroxy sulfide-containing ester can form anyhydroxy sulfide-containing ester as described herein.

In some aspects, the reaction between the mercaptan and the unsaturatedester occurs in the presence of a solvent. In other aspects the reactionbetween the mercaptan and the unsaturated ester occurs in thesubstantial absence of a solvent. When the reaction occurs in thepresence of a solvent, the solvent is selected from an aliphatichydrocarbon, an ether, an aromatic compound, or any combination thereof.Generally, the solvent, regardless of its chemical class, can comprisefrom 1 to 20 carbon atoms; alternatively, from 3 to 10 carbon atoms.When the solvent includes an aliphatic hydrocarbon, the aliphatichydrocarbon is butane, isobutane, pentane, hexane, heptane, octane, orany mixture thereof. When the solvent includes an aromatic compound, thearomatic compound is benzene, toluene, xylene, ethylbenzene, or anymixture thereof. When the solvent includes an ether, the ether isdiethyl ether, dipropyl ether, tetrahydrofuran, or any mixture thereof.

When a solvent is used for the reaction between the mercaptan and theepoxidized unsaturated ester, the quantity of solvent can be any amountthat facilitates the reaction, as understood by those of skill in theart. In some embodiments, the mass of the solvent is less than 30 timesthe mass of the epoxidized unsaturated ester. In other embodiments, themass of the solvent is less than 20 times the mass of the epoxidizedunsaturated ester; alternatively, less than 15 times the mass of theepoxidized unsaturated ester; alternatively, less than 10 times the massof the epoxidized unsaturated ester; or alternatively, less than 5 timesthe mass of the epoxidized unsaturated ester. In other embodiments, themass of the solvent is from 2 times to 20 times the mass of theepoxidized unsaturated ester; alternatively, from 3 times to 15 timesthe mass of the epoxidized unsaturated ester; alternatively, from 4times to 15 times the mass of the epoxidized unsaturated ester; oralternatively, from 5 times to 10 times the mass of the epoxidizedunsaturated ester.

The reaction of the mercaptan and the epoxidized unsaturated ester canoccur using any mercaptan to molar equivalents of epoxide groups in theepoxidized unsaturated ester (hereinafter referred to as “mercaptan toepoxide group molar ratio”) that is capable of producing the hereindescribed α-hydroxy thiol esters. The molar equivalents of epoxidizedunsaturated ester epoxidized groups can be calculated by the equation:

$\frac{{EUES}\mspace{14mu}{Mass}}{{EUES}\mspace{14mu}{GMW}} \times {EUES}\mspace{14mu}{Epoxide}$In this equation, EUES GMW is the average gram molecular weight of theepoxidized unsaturated ester, EUES Mass is the mass of the epoxidizedunsaturated ester, and EUES Epoxide is the average number of epoxidegroups per epoxidized unsaturated ester molecule. In some embodiments,the mercaptan to epoxide group molar ratio is greater than 0.2. In otherembodiments, the mercaptan to epoxide group molar ratio is greater than0.5; alternatively, greater than 1; or alternatively, greater than 2. Inother embodiments, the hydrogen sulfide to epoxide group molar ratioranges from 0.2 to 10; alternatively, from 0.5 to 8; alternatively, from0.75 to 5; or alternatively, from 1 to 3.

In some aspects, the reaction of the mercaptan and the epoxidizedunsaturated ester occurs in the presence of a catalyst. Generally, thecatalyst is any catalyst that is capable of catalyzing the reaction ofthe mercaptan and the epoxidized unsaturated ester to produce thedesired hydroxy thiol ester. In one aspect, the catalyst is selectedfrom the group consisting of homogeneous and heterogeneous catalysts. Inother aspects, the catalyst is selected from the group consisting ofzeolites, heterogeneous catalysts, homogeneous catalysts, and mixturesthereof. In another aspect, the catalyst is an amine. In other aspects,the catalyst is selected from the group consisting of cyclic conjugatedamines, 1,8-diazabicylco[5.4.0]undec-7-ene,1,5-diazabicylco[4.3.0]non-5-ene, and mixtures thereof.

In some aspects, the reaction of the mercaptan and the epoxidizedunsaturated ester occurs in the presence of a catalyst. Generally, thecatalyst is any catalyst that is capable of catalyzing the reaction ofthe mercaptan and the epoxidized unsaturated ester to produce thedesired hydroxy thiol ester. In some embodiments the catalyst is anorganic base. In some embodiments, the catalyst can be1,8-diazabicyclo[5.4.0]undec-7-ene. (What other catalysts may be used?)

The reaction of the mercaptan and the epoxidized unsaturated ester canoccur in a batch reactor of a continuous reactor. Any of the batch orcontinuous reactors described herein can be used in this reaction. Othersuitable reactors will be apparent to those of skill in the art and areto be considered within the scope of the present invention.

The time required for the reaction of the mercaptan and the epoxidizedunsaturated ester can be any reaction time required to form thedescribed hydroxy sulfide-containing ester. Generally, the reaction timeis at least 15 minutes. In some embodiments, the reaction time rangesfrom 15 minutes to 72 hours; alternatively, from 30 minutes to 48 hours;or alternatively, from 45 minutes to 36 hours.

In some embodiments, the process to produce the hydroxysulfide-containing ester further comprises a step to remove the residualmercaptan after reacting the mercaptan and the epoxidized unsaturatedester. In some embodiments the hydroxy sulfide-containing ester isvacuum stripped. In some embodiments, the hydroxy sulfide-containingester is vacuum stripped at a temperature between 25° C. and 250° C.; oralternatively, between 50° C. and 200° C. In other embodiments, thehydroxy sulfide-containing ester is sparged with an inert gas to removethe mercaptan. In some embodiments, the hydroxy sulfide-containing esteris sparged with an inert gas at a temperature between 25° C. and 250°C.; or alternatively, between 50° C. and 200° C. In some aspects, theinert gas is nitrogen. Generally, the stripped or sparged hydroxysulfide-containing ester comprises less than 5 weight percent of themercaptan. In other embodiments, the stripped or sparged hydroxysulfide-containing ester comprises less than 2 weight percent of themercaptan; alternatively, less than 1 weight percent of the mercaptan;or alternatively, less than 0.5 weight percent of the mercaptan.

The reaction between the mercaptan and the epoxidized unsaturated estercan be performed at any reaction temperature capable of forming thehydroxy sulfide-containing ester. In some embodiments, the reactiontemperature is greater than −20° C. In other embodiments, the reactiontemperature is greater than 0° C.; alternatively, greater than 20° C.;alternatively, greater than 50° C.; or alternatively, greater than 80°C. In yet other embodiments, the reaction temperature ranges from −20°C. to 200° C.; alternatively, from 20° C. to 170° C.; or alternatively,from 80° C. to 140° C.

The reaction between the mercaptan and the epoxidized unsaturated estercan be performed at any reaction pressure that maintains the mercaptanand the epoxidized unsaturated ester in a substantially liquid state. Insome embodiments, the reaction pressure ranges from 0 psig to 2000 psig.In other embodiments, the reaction pressure ranges from 0 psig to 1000psig; alternatively, from 0 psig to 500 psig; or alternatively, from 0psig to 200 psig.

In another aspect, the process to produce a hydroxy sulfide-containingester produces a hydroxy sulfide-containing ester having an epoxidegroup to sulfide group molar ratio less than 2. Other hydroxysulfide-containing ester epoxide group to sulfide group molar ratios aredescribed herein. (The next passage needs to be incorporated into thehydroxy thiol ester section along with the first sentence of thisparagraph.) Alternatively, the hydroxy sulfide-containing ester epoxidegroup to thiol group molar ratio can be less than 1.5; alternatively,less than 1.0; alternatively, less than 0.5; alternatively, less that0.25; or alternatively, less than 0.1. In other embodiments, the hydroxysulfide-containing ester can be substantially free of epoxide groups.

In another aspect, the process to produce hydroxy sulfide-containingester produces a hydroxy sulfide-containing ester wherein, at least 20percent of the side chains comprise a hydroxy sulfide group. Otherhydroxy sulfide-containing ester embodiments wherein the hydroxysulfide-containing ester contains a percentage of side chains comprisinga hydroxy sulfide groups are described herein. In other embodiments, theprocess to produce a hydroxy sulfide-containing ester produces a hydroxysulfide-containing ester composition comprising hydroxysulfide-containing ester molecules having an average of at least 20percent of the side chains contain the moiety Z. In other embodiments,the process to produce a hydroxy sulfide-containing ester produces ahydroxy sulfide-containing ester composition comprising hydroxysulfide-containing ester molecules having an average of at least 40percent of the total side chains contain the moiety Z; alternatively, atleast 60 percent of the total side chains comprise the moiety Z;alternatively, at least 70 percent of the total side chains comprise themoiety Z; or alternatively, at least 80 percent of the total side chainscomprise the moiety Z. (Incorporate the moiety Z embodiments (and moietyX and Y embodiments) into the sulfide-containing ester compositionsection.

Process for Producing a Sulfonic Acid-Containing Ester or aSulfonate-Containing Ester

As an embodiment of the present invention, processes for producing asulfonic acid-containing ester and for producing a sulfonate-containingester are advantageously provided. Generally, the process for producingthe sulfonic acid-containing ester comprises the steps of contacting athiol ester and an oxidizing agent and oxidizing at least one thiolgroup of the thiol ester to produce a sulfonic acid group. The processfor producing the sulfonate-containing ester comprises the steps ofcontacting a sulfonic acid-containing ester with a base and forming asulfonate-containing ester.

Process for Producing a Sulfonic Acid-containing Ester

In an embodiment, the process to prepare a sulfonic acid-containingester comprises the steps of contacting the thiol ester and theoxidizing agent and oxidizing the thiol ester to produce the sulfonicacid-containing ester. Generally the oxidizing agent oxidizes at leastone thiol group of the thiol ester to a sulfonate group. The process toproduce the sulfonic acid-containing ester composition can be applied toany thiol ester described herein to prepare any sulfonic acid-containingester described herein. In some embodiments, the thiol ester includes ahydroxy group. For example, the thiol ester can be any hydroxy thiolester described herein. The oxidizing agent can be any oxidizing agentdescribed herein.

In some aspects, the oxidation of the thiol ester occurs in the presenceof a solvent, In some aspects, the solvent is water.

The oxidizing agent that is contacted with the thiol ester can be anyoxidizing agent capable of oxidizing a thiol group to a sulfonic acidgroup. In some embodiments, the oxidizing agent is oxygen. In otherembodiments, the oxidizing agent is chlorine. In other embodiments, theoxidizing agent is dimethyl sulfoxide. In yet other embodiments, theoxidizing agent is a combination of a hydrogen halide and a catalyticamount of a dialkyl sulfide, such as dimethyl sulfoxide. Other suitableoxidizing agents will be apparent to those of skill in the art and areto be considered within the scope of the present invention.

The oxidation of the thiol ester can be performed at any temperaturecapable of converting the thiol ester to a sulfonic acid-containingester. In some embodiments, the thiol ester is oxidized a temperaturegreater than −20° C. In other embodiments, the thiol ester is oxidizedat a temperature greater than 0° C.; alternatively, greater than 20° C.;or alternatively, greater than 50° C.

The time required for the oxidation of the thiol ester can be any timerequired to form the desired sulfonic acid-containing ester. Generally,the time required for the oxidation of the thiol ester is at least 15minutes; alternatively, at least 30 minutes; alternatively, at least 45minutes; or alternatively, at least 1 hour. In some embodiments, thetime required for the oxidation of the thiol ester ranges from 15minutes to 12 hours; alternatively, from 30 minutes to 6 hours;alternatively, from 45 minutes to 3 hours.

The oxidation of the thiol ester can be performed at any pressure thatmaintains the thiol ester and the oxidation agent in the proper state,which is not always a liquid state, to oxidize the thiol ester to asulfonic acid-containing ester. For example, when the oxidation agent ischlorine, the chlorine can be in the gaseous state. In some embodiments,the oxidation of the thiol ester can performed at a pressure rangingfrom 0 psig to 2000 psig. In other embodiments, the oxidation of thethiol ester can be performed at a pressure ranging from 0 to 1000 psig;or alternatively, 0 to 500 psig.

The oxidation of the thiol ester can be performed in a batch reactor ora continuous reactor, as described herein. Additionally, the process toproduce the sulfonic acid-containing ester can comprise additionalprocess steps as recognized by those skilled in the art.

Process for Producing a Sulfonate-Containing Ester

In an aspect of the present invention, a process to produce thesulfonate-containing ester is advantageously provided. In an embodiment,the process to prepare a sulfonate-containing ester comprises the stepsof contacting the sulfonic acid-containing ester and a base and formingthe sulfonate-containing ester composition. The process to produce thesulfonate-containing ester can be applied to any sulfonicacid-containing ester described herein to prepare anysulfonate-containing ester described herein. In some aspects, theprocess to prepare the sulfonate-containing ester includes the steps ofthe process to prepare the sulfonic acid-containing ester, which aredescribed herein, in addition to the steps of producing thesulfonate-containing ester.

In some aspects, the formation of the sulfonate-containing ester occursin the presence of a solvent. In some aspects, the solvent is water.

In some aspects, the base can be a metal hydroxide. In some embodiments,the metal hydroxide is selected from the group consisting of sodium,potassium, barium, calcium, magnesium, and mixtures thereof. Inparticular embodiments, the metal hydroxide is sodium hydroxide. Inother aspects, the metal hydroxide is calcium hydroxide or magnesiumhydroxide. In yet other aspects, the metal hydroxide is bariumhydroxide. In other aspects, the base is an organic amine. In someembodiments, the amine has the structure NRs3Rs4Rs5 wherein Rs3, Rs4,and Rs5 are independently selected from hydrogen, C1 to C10 organylgroups, and C1 to C10 hydrocarbyl groups. In other embodiments, theorganic amine is a trialkylamine, a dialkylamine, or a monoalkylamine.In a particular embodiment, NRs3Rs4Rs5 represents triethanolamine.

The formation of the sulfonate-containing ester can be performed at anytemperature capable of converting the sulfonic acid group of thesulfonic acid-containing ester to a sulfonate group. In someembodiments, the sulfonate-containing ester is formed at a temperaturegreater than −20° C. In other embodiments, the thiol ester is oxidizedat a temperature greater than 0° C.; alternatively, greater than 20° C.;or alternatively, greater than 50° C. In yet other embodiments, thethiol ester is oxidized at a temperature ranging from 0° C. to 250° C.;alternatively, from 0° C. to 150° C.; or alternatively, from 20° C. to100° C.

The time required for the formation of the sulfonate-containing estercan be any time required to converting the sulfonic acid group of thesulfonic acid-containing ester to a sulfonate group. Generally, the timerequired for the formation of the sulfonate-containing ester is at least15 minutes; alternatively, at least 30 minutes; alternatively, at least45 minutes; or alternatively, at least 1 hour. In some embodiments, thetime required for the formation of the sulfonate-containing ester rangesfrom 15 minutes to 12 hours; alternatively, from 30 minutes to 6 hours;alternatively, from 45 minutes to 3 hours.

The formation of the sulfonate-containing ester can be performed at anypressure that maintains the sulfonic acid-containing ester, base, andoptional solvent in a liquid state. In some embodiments the formation ofthe sulfonate-containing ester is performed at a pressure ranging from 0psig to 2000 psig. In other embodiments, the formation of thesulfonate-containing ester is performed at a pressure ranging from 0 to1000 psig; or alternatively, 0 to 500 psig.

In one aspect the process to prepare a sulfonate-containing ester isperformed as a batch process. In another aspect the process to prepare asulfonate-containing ester is performed as a continuous process.

Polythiourethane and/or Epoxy Polymer Encapsulated Controlled ReleaseFertilizer Material.

Thus, in one of its aspects, the present invention relates to apolythiourethane and/or epoxy polymer encapsulated controlled releasefertilizer material. The terms “controlled release fertilizer material”and “CRF material” are used interchangeably throughout thisspecification and are intended to have the same meaning. Further, asused throughout this specification, the term “vegetable oil” is intendedto have a broad meaning an includes fatty acid triglyceride sources suchas soybean oil, corn oil, canola oil, rapeseed oil and the like. Themost preferred vegetable oil for use herein is soybean oil.

Generally, the fertilizer material comprises a particulate plantnutrient material. The choice of particulate plant nutrient materialuseful for the present CRF material is not particularly restricted andis within the purview of a person skilled in the art.

For example, the plant nutrient material used may be selected from thosedisclosed in Hudson. Preferably, such a plant nutrient comprises a watersoluble compound, more preferably a compound containing at least onemember selected from the group consisting of nitrogen, phosphorus,potassium, sulfur, micronutrients and mixtures thereof. A preferred suchplant nutrient comprises urea. Other useful examples of plant nutrientsare taught in U.S. Pat. No. 5,571,303 [Bexton] and/or U.S. Pat. No.6,663,686 [Geiger et al.]—e.g., ammonium sulfate, ammonium phosphate andmixtures thereof. Non-limiting examples of useful micronutrients may beselected from the group comprising copper, zinc, boron, manganese, ironand mixtures thereof.

Preferably, the coating surrounds the plant nutrient material in anamount in the range of from about 0.1 to about 20 percent by weight,more preferably from about 2.0 to about 15 percent by weight, and mostpreferably from about 2.5 to about 10 percent by weight, based on theweight of the plant nutrient material.

In a preferred embodiment of the present invention, thesulfur-containing vegetable oil as the sole active hydrogen-containingcompound for reaction with the isocyanate (e.g., in the case where thedesired coating is a polythiourethane) or for reaction with the epoxyresin component (i.e., in the case where the desired coating is a epoxypolymer). Alternatively, it is possible to use a combination of thesulfur-containing vegetable oil and another active hydrogen-containingcompound—e.g., a polyol.

The choice of polyol is not particularly restricted and is within thepurview of a person skilled in the art. A polyol here refers to anactive hydrogen containing compound reactive with isocyanate. The polyolmay be a single type of polyol or a mixture of different polyols. Forexample, the polyol may be a hydroxyl-terminated backbone of a memberselected from the group comprising polyether, polyester, polycarbonate,polydiene and polycaprolactone. Preferably, such a polyol is selectedfrom the group comprising hydroxyl-terminated polyhydrocarbons, fattyacid triglycerides, hydroxyl-terminated polyesters,hydroxymethyl-terminated polyesters, hydroxymethyl-terminatedperfluoromethylenes, polyalkyleneether glycols, polyalkylenearyleneetherglycols and polyalkyleneether triols. More preferred polyols areselected from the group comprising polyethylene glycols, adipicacid-ethylene glycol polyester, poly(butylene glycol), poly(propyleneglycol) and hydroxyl-terminated polybutadiene—see, for example, Britishpatent No. 1,482,213. The most preferred such polyol is a polyetherpolyol. Preferably, such a polyether polyol has a molecular weight inthe range of from about 60 to about 20,000, more preferably from about60 to about 10,000, and most preferably from about 60 to about 8,000.

If used, a particularly preferred class of polyols are polyolscomprising from about 2 to about 12 hydroxyl moieties. Preferably, suchpolyols are those with low equivalent weight and high functionality. Thepreferred equivalent weight is 29-400. More preferably, the equivalentweight is 29-200. Most preferably, the equivalent weight is 29-150. Thefunctionality of the polyol as used herein refers to the preferredfunctionality of the basic unit (or monomer). Preferably, thefunctionality of the polyol is between about 2 and about 12, morepreferably between about 3 and about 8, and most preferably betweenabout 3 and about 6. More preferably, such a polyether polyol is made byusing an amine as initiator. Most preferably, the polyol comprises amixture of Huntsman Jeffol A480™ and another polyol, preferably, castoroil.

Additionally, the polyol, if used, may be derived from fatty acidtriglyceride sources such as soybean, corn, canola and the like (i.e.,to produce naturally occurring modified oils). An example of such asynthetic polyol comprising a canola base is commercially available fromUrethane Soy Systems Corp. (Princeton, Illinois) with a functionality ofabove 3. A mixture of polyols with a prescribed ratio and molecularweight distribution may be used, for example, Huntsman Jeffol A480™ or800™ with ethylene glycol, Huntsman Jeffol A480™ or 800™ with oleopolyol, Huntsman Jeffol A480™ or 800™ with polyethylene glycol, HuntsmanJeffol A480™ or 800™ with polypropylene glycol, Huntsman Jeffol A480™ or800™ with a polypropylene (or polyethylene) glycol mixture of differentfunctionality and molecular weight.

The isocyanate suitable for use in producing the coating is notparticularly restricted and the choice thereof is within the purview ofa person skilled in the art. The isocyanate may be a single type ofisocyanate or a mixture of different isocyanates. Generally, theisocyanate compound suitable for use may be represented by the generalformula:Q(NCO)iwherein i is an integer of two or more and Q is an organic radicalhaving the valence of i. Q may be a substituted or unsubstitutedhydrocarbon group (e.g. an alkylene or arylene group). Moreover, Q maybe represented by the general formula:Q1-Z-Q1wherein Q1 is an alkylene or arylene group and Z is chosen from thegroup comprising —O—, —O-Q1-, —CO—, —S—, —S-Q1-S— and —SO₂—. Examples ofisocyanate compounds which fall within the scope of this definitioninclude hexamethylene diisocyanate, 1,8-diisocyanato-p-naphthalene,xylyl diisocyanate, (OCNCH2CH2CH₂OCH₂O)2,1-methyl-2,4-diisocyanatocyclohexane, phenylene diisocyanates, tolylenediisocyanates, chlorophenylene diisocyanates,diphenylmethane-4,4□-diisocyanate, naphthalene-1,5-diisocyanate,triphenylmethane-4,4□,4□-triisocyanate andisopropylbenzene-alpha-4-diisocyanate.

In another embodiment, Q may also represent a polyurethane radicalhaving a valence of i. In this case Q(NCO)i is a compound which iscommonly referred to in the art as a prepolymer. Generally, a prepolymermay be prepared by reacting a stoichiometric excess of an isocyanatecompound (as discussed hereinabove) with the sulfur-containing vegetableoil (discussed hereinabove) and/or the polyol (discussed hereinabove).In this embodiment, the polyisocyanate may be, for example, used inproportions of from about 5 percent to about 200 percent stoichiometricexcess with respect to the proportion of active hydrogen in thesulfur-containing vegetable oil and/or the polyol.

The isocyanate compound suitable for use in the process of the presentinvention also may be selected from dimers and trimers of isocyanatesand diisocyanates, and from polymeric diisocyanates having the generalformula:[Q″(NCO)_(i)]_(j)wherein both i and j are integers having a value of 2 or more, and Q″ isa polyfunctional organic radical, and/or, as additional components inthe reaction mixture, compounds having the general formula:L(NCO)_(i)wherein i is an integer having a value of 1 or more and L is amonofunctional or polyfunctional atom or radical. Examples of isocyanatecompounds which fall with the scope of this definition includeethylphosphonic diisocyanate, phenylphosphonic diisocyanate, compoundswhich contain a ═Si—NCO group, isocyanate compounds derived fromsulphonamides (QSO₂NCO), cyanic acid and thiocyanic acid.

See also, for example, British patent No. 1,453,258.

Non-limiting examples of suitable isocyanates include: 1,6-hexamethylenediisocyanate, 1,4-butylene diisocyanate, furfurylidene diisocyanate,2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 2,4′-diphenylmethanediisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenylpropanediisocyanate, 4,4′-diphenyl-3,3′-dimethyl methane diisocyanate,1,5-naphthalene diisocyanate, 1-methyl-2,4-diisocyanate-5-chlorobenzene,2,4-diisocyanato-s-triazine, 1-methyl-2,4-diisocyanato cyclohexane,p-phenylene diisocyanate, m-phenylene diisocyanate, 1,4-naphthalenediisocyanate, dianisidine diisocyanate, bitoluene diisocyanate,1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate,bis-(4-isocyanatophenyl)methane,bis-(3-methyl-4-isocyanatophenyl)methane, polymethylene polyphenylpolyisocyanates and mixtures thereof.

A particularly preferred group of isocyanates are those described inHudson and Markusch.

Preferably, the isocyanate contains from about 1.5 to about 16 NCOgroups per molecule. More preferably, the isocyanate contains from about2 to about 16 NCO groups per molecule. Most preferably, the isocyanatecontains from about 3 to about 16 NCO groups per molecule.

Preferably, the isocyanate contains from about 10 to about 50 percentNCO by weight. More preferably, the isocyanate contains from about 12 toabout 50 percent NCO by weight. Most preferably, the isocyanate containsfrom about 15 to about 50 percent NCO by weight.

The sulfur-containing vegetable oil for use in the present CRF materialis preferably selected those described in detail herein.

A preferred sulfur-containing vegetable oil is MVO available fromChevron Phillips Chemical Co. under the tradename Polymercaptan 358.Polymercaptan 358 is made by the free radical addition of hydrogensulfide to the double bonds in soybean oil. Typically, Polymercaptan 358has a thiol sulfur content of 5 to 10% and equivalent weights of 640 to320, respectively.

Another preferred sulfur-containing vegetable oil useful as part of theisocyanate-reactive component is a MHVO such as mercapto-hydroxy soybeanoil. As described herein, a preferred mercapto-hydroxy soybean oil ismade by the free radical addition of hydrogen sulfide to epoxidizedsoybean oil. Typically, the mercapto and hydroxy functionalities areequal and the mercaptan content is about 8.3% thiol sulfur. Theequivalent weight of this material is 192, which includes both mercaptoand hydroxy functionalities.

Yet another preferred sulfur-containing vegetable oil useful as part ofthe isocyanate-reactive component is a CMVO such as sulfur cross-linkedmercaptanized soybean oil. Sulfur cross-linked mercaptanized soybean oilis made by the addition of elemental sulfur to mercaptanized soybeanoil. In this process, a portion of the mercaptan groups are consumed ascross-linking sites for the sulfur. Typical sulfur cross-linkedmercaptanized soybean oil products by Chevron Phillips Chemical Co.include Runs #22, 194, 195, 196 and 197 and have a thiol sulfur contentranging from about 8.0% to 1.4% and equivalent weights ranging fromabout 400 to about 2250, respectively.

Other isocyanate-reactive components can be used in conjunction with thesulfur-containing vegetable oil in order to increase the cross-linkdensity of the polythiourethane coating. Examples, but not limiting toone skilled in the art for cross-linking agents, include low molecularweight polyethylene and polypropylene glycols, amine initiatedpolyethylene and polypropylene glycols, aromatic amine inititatedpolyethylene and propylene glycols, glycerol, sorbitol, neopentylglycol, ethylene diamine and toluene diamine. The amount and choice ofcross-linking agent used is within purview of a person of ordinary skillin the art and is dependent upon the desired physical properties of thecoating.

The use of a catalyst for the reaction of the sulfur-containingvegetable oils with the isocyanate is conventional. The selection of thecatalyst is within the purview of a person of ordinary skill in the art.Examples, but not limiting, of suitable catalysts include tertiaryamines and organo-tin compounds. Particularly useful catalysts are amineinitiated polypropylene glycols since they also act as cross-linkingagents along with their catalytic effect.

Organic additives can be optionally added to the formulation for coatingthe CRF material to increase the hydropobicity and/or the handlingdurability of the coating, if desired. The organic additive can be addedto either the isocyanate-reactive component or the polyisocyanatecomponent, prior to applying them to the fertilizer particles. Suitableorganic additives include, but not limited to, waxes, both synthetic andnatural, petrolatums, asphalts, fatty acids, fatty acid salts, fattyacid esters, higher alcohols, silicones and mixtures thereof. Aparticularly useful organic additive is synthetic alpha olefin wax(e.g., a C₂₀₊ alpha olefin wax) made by Chevron Phillips Chemical Co.Another useful organic additive is a microcrystalline wax, such asCalwax™ 170, available from Calwax Corp.

Preferably, the addition of an organic additive or mixture of organicadditives is in an amount of up to about 90% by weight of the coating,preferably in the range of from about 0.1% to about 90% by weight of thecoating, more preferably in the range of from about 1% to about 80% byweight of the coating and most preferably in the range of from about 2%to 50% by weight of the coating.

It is also possible to include other additives in either theisocyanate-reactive component or the polyisocyanate component, prior toapplying them to the fertilizer particles. Possible additives include,for example, flow aids, surfactants, defoamers and other additives knowto those of ordinary skill in the art. Any additive, which aids theformation of the polythiourethane coating that encapsulates thefertilizer particles, may be included in one or both of thesecomponents.

Suitable epoxy resins to be used in conjunction with mercaptanizedvegetable oil for the purpose of this invention include, but not limitedto, liquid bisphenol A diglycidyl ethers, such as Dow Plastics D.E.R.331 and 324, and Resolution Performance Products Epon Resin 282 and 8121and mixtures thereof. Also, epoxidized soybean oil can be used, such ascommercially available AtoChem Vikoflex 7170 and mixtures thereof withother epoxy resins.

For epoxy polymer encapsulated CRF material made from sulfur-containingvegetable oil, it has been found that the use of a tertiary aminecatalyst is highly preferred. The amount used is such to be sufficientto give the desired reaction rate for the production of the encapsulatedslow release fertilizer product. A non-limiting example of a suitableamine catalyst is diazobicycloundecacene also known as1,8-diazabicyclo[5,4,0]undec-7-ene [CAS# 6674-22-2] or “DBU”, which ispreferably used in the range of about 0.1% to 0.5% by weight of thecoating. Other suitable catalyst materials will be apparent to those ofordinary skill in the art.

Preferably the amine catalyst is premixed with the sulfur-containingvegetable oil and then this mixture along with the epoxy resin isapplied to the fertilizer particles, either simultaneously or either onebefore the other.

The preferred sulfur-containing vegetable oil to be used in productionof an epoxy polymer coated CRF material is MHVO such as mercapto-hydroxysoybean oil. One such material is mercapto-hydroxy soybean oil known asMHSO 566-84 produced by Chevron Phillips Chemical Co. This preferredmaterial contains 8.33% thiol sulfur, with an equivalent weight of 384,based upon the mercaptan functionality.

Organic additives can be optionally added to the formulation to increasethe hydropobicity and/or the handling durability of the epoxy polymercoating, if desired. The organic additive can be added to either theepoxy-reactive component and/or the sulfur-containing vegetablecomponent, prior to applying them to the fertilizer particles. Suitableorganic additives include, but not limited to, waxes, both synthetic andnatural, petrolatums, asphalts, fatty acids, fatty acid salts, fattyacid esters, higher alcohols, silicones and mixtures thereof. Aparticularly useful organic additive is synthetic alpha olefin wax madeby Chevron Phillips Chemical Co.

Preferably, the addition of an organic additive or mixture of organicadditives for use with the epoxy polymer is in an amount of up to about90% by weight of the coating, preferably in the range of from about 0.1%to about 90% by weight of the coating, more preferably in the range offrom about 1% to about 80% by weight of the coating and most preferablyin the range of from about 2% to 50% by weight of the coating.

It is also possible to include other additives in either theepoxy-reactive component (the sulfur-containing vegetable oil) or theepoxy resin component, prior to applying them to the fertilizerparticles. Possible additives include, for example, flow aids,surfactants, defoamers and other additives known to those of ordinaryskill in the art. Any additive, which aids the formation of the epoxypolymer coating that encapsulates the fertilizer particles, may beincluded in one or both of these components.

According to a preferred embodiment, the present CRF material may beproduced by applying the isocyanate-reactive component along with thepolyisocyanate component at ambient temperature (e.g., from about 20° C.to about 30° C.). Preferably, the fertilizer particles are preheated toa temperature in the range of from about 50° C. to 100° C., morepreferably from about 60° C. to 80° C.

According to another preferred embodiment of the invention, the presentCRF material may be produced by applying the epoxy-resin reactivecomponents, containing the amine catalyst, along with the epoxy resincomponent at ambient temperature (e.g., from about 20° C. to about 30°C.) Preferably, the fertilizer particles are preheated to a temperaturein the range of from about 50° C. to 100° C., more preferably from about60° C. to 80° C.

During the coating operation, it is preferred to use a device thatmaintains the fertilizer particles in a continuous low shear, lowimpact, motion relative to each other. Examples of suitable mixingapparatus include fluid bed, rotating drum, pan pelletizer and the likethat can provide a continuous low shear, motion of the fertilizerparticles.

Preferably, polythiourethane encapsulated CRF material may be producedby carrying out the following steps: (i) providing a quantity offertilizer particles, (ii) agitating the fertilizer particles such thata gentle mixing thereof is maintained, (iii) adding to the agitatedfertilizer particles an isocyanate-reactive component comprising thesulfur-containing vegetable oil (with or without one or more ofcross-linking agents, hydrophobic organic additives or other additivesas described above), (iv) adding to the agitated fertilizer particles anisocyanate (with or without one or more of hydrophobic organic additivesor other additives as described above), in such an amount that the ratioof NCO groups to isocyanate-reactive functional groups is from about0.8:1, to about 2.0:1, preferably from about 0.9:1 to about 1.5:1 andmost preferably from about 0.95 to about 1.3:1, (v) allowing isocyanateand isocyanate-reactive component to react, thus forming a solidifiedpolythiourethane coating on the surface of the fertilizer particles, and(vi) cooling the coated fertilizer particles to about or slightly aboveroom temperature, with continuous, gentle agitation.

If multiple coating layers are required to achieve the desired slowrelease fertilizer, Steps (ii) through (vi) can be repeated a number oftimes (e.g., from 2 to 10 times).

In accordance with the CRF material of the present invention, it is notnecessary that the fertilizer particles contain isocyanate-reactivefunctional groups.

Polythiourethane encapsulation of the fertilizer particles to obtain thea prescribed release rate profile of the fertilizer depends on a numberof factors, including: (i) correct metering of the co-reactants andadditives, (ii) relatively precise temperature control, (iii)substantially continuous movement of the fertilizer particles in agentle, low shear environment, (iv) proper selection of type and amountof catalyst to ensure complete reaction of the isocyanate-reactivecomponents with the polyisocyanate component before successive layersare applied (assuming multiple layers are being applied), and/or (v)cooling of the coated fertilizer particles to avoid agglomeration of thefinal product.

In accordance with a preferred embodiment, the sulfur-containingvegetable oil, along with the hydrophobic organic additive (if present),is applied as a separate stream to the fertilizer particles, prior tothe addition of the isocyanate. Also, preferably, the catalyst andcross-linking agent, if any, are added as a separate stream to thefertilizer particles. The order of addition is not important and iswithin the purview of one skilled in the art.

Preferably, epoxy polymer encapsulated CRF material may be produced bycarrying out the following steps: (i) providing a quantity of fertilizerparticles, (ii) agitating the fertilizer particles such that a gentlemixing thereof is maintained, (iii) adding to the agitated fertilizerparticles an epoxy-reactive component comprising a sulfur-containingvegetable oil (with or without one or more of the hydrophobic organicadditives and other additives as described above), (iv) adding to theagitated fertilizer particles an epoxy resin component (with or withoutone or more hydrophobic organic additives and other additives asdescribed above), in such an amount that the ratio of oxirane groups inthe epoxy resin to epoxy-reactive functional groups is from about 0.8:1,to about 2.0:1, preferably from about 0.9:1 to about 1.5:1; evenpreferably from about 0.95 to about 1.3:1 and most preferably from about0.95 to about 1.05:1, (v) allowing the epoxy resin and epoxy-reactivematerials to react, thus forming a solidified epoxy polymer coating onthe surface of the fertilizer particles, and (vi) cooling the coatedfertilizer particles to about or slightly above room temperature, withcontinuous, gentle agitation.

If multiple coating layers are required to achieve the desired slowrelease fertilizer, Steps (ii) through (vi) can be repeated a number oftimes (e.g., 2 to 10 times).

Epoxy polymer encapsulation of the fertilizer particles to obtain the aprescribed release rate profile of the fertilizer depends on a number offactors, including: (i) correct metering of the co-reactants andadditives, (ii) relatively precise temperature control, (iii)substantially continuous movement of the fertilizer particles in agentle, low shear environment, (iv) proper selection of type and amountof catalyst to ensure complete reaction of the epoxy-reactive componentswith the epoxy resin component before successive layers are applied(assuming multiple layers are being applied), and (v) cooling of thecoated fertilizer particles to avoid agglomeration of the final product.

In accordance with a preferred embodiment, the sulfur-containingvegetable oil, along with hydrophobic organic additive (if present), isapplied as a separate stream to the fertilizer particles, prior to theaddition of the epoxy resin component. Also, preferably, the catalystand other additives, if any, are added as a separate stream to thefertilizer particles. The order of addition is not important and iswithin the purview of one skilled in the art.

In a further embodiment of this invention, a combination of epoxypolymer layers and polythiourethane layers can be applied to fertilizerparticles to give a composite polymer coating for the CRF material. Theepoxy polymer coating and polythiourethane coating can be applied in anyorder.

Feedstocks

Unsaturated Ester

The unsaturated ester used as a feedstock to produce the thiol estercompositions described herein can be described using a number ofdifferent methods. One method of describing the unsaturated esterfeedstock is by the number of ester groups and the number ofcarbon-carbon double bonds that comprise each unsaturated ester oilmolecule. Suitable unsaturated ester used as a feedstock to produce thethiol ester compositions described herein minimally comprise at least 1ester group and at least 1 carbon-carbon double bond. However, beyondthis requirement, the number of ester groups and carbon-carbon doublebonds comprising the unsaturated esters are independent elements and canbe varied independently of each other. Thus, the unsaturated esters canhave any combination of the number of ester groups and the number ofcarbon-carbon double bonds described separately herein. Suitable,unsaturated esters can also contain additional functional groups such asalcohol, aldehyde, ketone, epoxy, ether, aromatic groups, andcombinations thereof. As an example, the unsaturated esters can alsocomprise hydroxy groups. An example of an unsaturated ester thatcontains hydroxy groups is castor oil. Other suitable unsaturated esterswill be apparent to those of skill in the art and are to be consideredwithin the scope of the present invention.

Minimally the unsaturated ester comprises at least one ester group. Inother embodiments, the unsaturated ester comprises at least 2 estergroups. Alternatively, the unsaturated ester comprises 3 ester groups.Alternatively, the unsaturated ester comprises 4 ester groups.Alternatively, the unsaturated ester includes from 2 to 8 ester groups.Alternatively, the unsaturated ester includes from 2 to 7 ester groups.Alternatively, the unsaturated ester includes from 3 to 5 ester groups.As another alternative, the unsaturated ester includes from 3 to 4 estergroups.

In other embodiments, the unsaturated ester comprises a mixture ofunsaturated esters. In these situations, the number of ester groups isbest described as an average number of ester groups per unsaturatedester molecule comprising the unsaturated ester composition. In someembodiments, the unsaturated esters have an average of at least 1.5ester groups per unsaturated ester molecule; alternatively, an averageof at least 2 ester groups per unsaturated ester molecule;alternatively, an average of at least 2.5 ester groups per unsaturatedester molecule; or alternatively, an average of at least 3 ester groupsper unsaturated ester molecule. In other embodiments, the unsaturatedesters have an average of from 1.5 to 8 ester groups per unsaturatedester molecule; alternatively, an average of from 2 to 7 ester groupsper unsaturated ester molecule; alternatively, an average of from 2.5 to5 ester groups per unsaturated ester molecule; alternatively, an averageof from 3 to 4 ester groups per unsaturated ester molecule. In anotherembodiment, the unsaturated esters have an average of about 3 estergroups per unsaturated ester molecule or alternatively, an average ofabout 4 ester groups per unsaturated ester molecule.

Minimally, the unsaturated ester comprises at least one carbon-carbondouble bond per unsaturated ester molecule. In an embodiment theunsaturated ester comprises at least 2 carbon-carbon double bonds;alternatively, at least 3 carbon-carbon double bonds; or alternatively,at least 4 carbon-carbon double bonds. In other embodiments, theunsaturated ester comprises from 2 to 9 carbon-carbon double bonds;alternatively, from 2 to 4 carbon-carbon double bonds; alternatively,from 3 to 8 carbon-carbon double bonds; or alternatively, from 4 to 8carbon-carbon double bonds.

In some embodiments, the unsaturated ester comprises a mixture ofunsaturated esters. In this aspect, the number of carbon-carbon doublebonds in the mixture of unsaturated ester is best described as anaverage number of carbon-carbon double bonds per unsaturated ester oilmolecule. In some embodiments, the unsaturated esters have an average ofat least 1.5 carbon-carbon double bonds per unsaturated ester molecule;alternatively, an average of at least 2 carbon-carbon double bonds perunsaturated ester molecule; alternatively, an average of at least 2.5carbon-carbon double bonds per unsaturated ester molecule; oralternatively, an average of at least 3 carbon-carbon double bonds perunsaturated ester molecule. In other embodiments, the unsaturated estershave average of from 1.5 to 9 carbon-carbon double bonds per unsaturatedester molecule; alternatively, an average of from 3 to 8 carbon-carbondouble bonds per unsaturated ester molecule; alternatively, an averageof from 2 to 4 carbon-carbon double bonds per unsaturated estermolecule; or alternatively, from of 4 to 8 carbon-carbon double bondsper unsaturated ester molecule.

While the number (or average number) of ester groups and the number (oraverage number) double bonds are independent elements of the unsaturatedesters, particular embodiments are mentioned for illustrative purposes.In an embodiment, the unsaturated ester molecules have an average of atleast 1.5 ester groups per unsaturated ester molecule and have anaverage of at least 1.5 carbon-carbon double bonds per unsaturated estermolecule. Alternatively, the unsaturated ester molecules have an averageof at least 3 ester groups per unsaturated ester molecule and have anaverage of at least 1.5 carbon-carbon double bonds per unsaturated estermolecule. Alternatively, the unsaturated ester molecules have an averageof at least 3 ester groups per unsaturated ester molecule and have anaverage of from 1.5 to 9 carbon-carbon double bonds per unsaturatedester molecule. As another alternative, the unsaturated ester moleculeshave an average of from 2 to 8 ester groups per unsaturated estermolecule and have an average of from 1.5 to 9 carbon-carbon double bondsper unsaturated ester oil.

In addition to the number (or average number) of ester groups and thenumber (or average number) of carbon-carbon double bonds present in theunsaturated ester molecules, the disposition of the carbon-carbon doublebonds in unsaturated ester molecules having 2 or more carbon-carbondouble bonds can be a consideration. In some embodiments where theunsaturated ester molecules have 2 or more carbon-carbon double bonds,the carbon-carbon double bonds can be conjugated. In other embodiments,the carbon-carbon double bonds can be separated from each other by onlyone carbon atom. When two carbon-carbon double bonds are separated by acarbon atom having two hydrogen atoms attached to it, e.g. a methylenegroup, these carbon-carbon double bonds can be termed as methyleneinterrupted double bonds. In yet other embodiments, the carbon-carbondouble bonds are isolated, e.g. the carbon-carbon double bonds areseparated from each other by 2 or more carbon atoms. In furtherembodiments, the carbon-carbon double bonds can be conjugated with acarbonyl group.

In some aspects, the unsaturated ester may be described as an ester of apolyol and unsaturated carboxylic acids. Within this description, theunsaturated carboxylic acid portion of the unsaturated ester can becalled a polyol side chain (or more simply a side chain). In someembodiments, the unsaturated ester comprises less than 30 percent ofside chains comprising methylene interrupted double bonds. In otherembodiments, embodiments the unsaturated ester comprises greater than 30percent of the side chains comprise methylene interrupted double bonds.In yet other embodiments, the unsaturated ester comprises less than 25percent of side chains having 3 contiguous methylene interruptedcarbon-carbon double bonds. In further embodiments, the unsaturatedester comprises less than 25 percent linolenic acid side chains. Infurther embodiments, the unsaturated ester comprises greater than 25percent of side chains having 3 contiguous methylene interruptedcarbon-carbon double bonds. In further embodiments, the unsaturatedester comprises greater than 25 percent linolenic acid side chains. Inadditional embodiments, the unsaturated ester comprises at least 30percent side chains having 2 contiguous methylene interruptedcarbon-carbon double bonds and less than 25 percent of side chainshaving 3 contiguous methylene interrupted carbon-carbon double bonds.

Additional functional groups can also be present in the unsaturatedester. A non-limiting list of functional groups include a hydroxy group,an ether group, aldehyde group, a ketone group, an amine group, acarboxylic acid group among others, and combinations thereof. In anaspect, the unsaturated ester can comprise hydroxy groups. In someembodiments, the unsaturated esters have an average of at least 1.5hydroxy groups per unsaturated ester molecule; alternatively, an averageof at least 2 hydroxy groups per unsaturated ester molecule;alternatively, an average of at least 2.5 hydroxy groups per unsaturatedester molecule; or alternatively, an average of at least 3 hydroxygroups per unsaturated ester molecule. In other embodiments, theunsaturated esters have average of from 1.5 to 9 hydroxy groups perunsaturated ester molecule; alternatively, an average of from 3 to 8hydroxy groups per unsaturated ester molecule; alternatively, an averageof from 2 to 4 hydroxy groups per unsaturated ester molecule; oralternatively, from of 4 to 8 hydroxy groups per unsaturated estermolecule. In an embodiment the unsaturated ester comprises at least 2hydroxy groups; alternatively, at least 3 hydroxy groups; oralternatively, at least 4 hydroxy groups. In other embodiments, theunsaturated ester comprises from 2 to 9 hydroxy groups; alternatively,from 2 to 4 hydroxy groups; alternatively, from 3 to 8 hydroxy groups;or alternatively, from 4 to 8 hydroxy groups.

Sources of Unsaturated Ester Oils

The unsaturated ester oil utilized as a feedstock of this invention canbe any unsaturated ester oil having the number of ester groups andcarbon-carbon double bonds per unsaturated ester oil described herein.The unsaturated ester oil can be derived from natural sources,synthetically produced from natural source raw materials, produced fromsynthetic 115 raw materials, produced from a mixture of natural andsynthetic materials, or a combination thereof.

Unsaturated Natural Source Oil

In an embodiment, the unsaturated ester oil is unsaturated naturalsource oil. The unsaturated natural source oil can derived fromnaturally occurring nut, vegetable, plant and animal sources. In anembodiment, the unsaturated ester oil is derived from geneticallymodified nuts, vegetables, plant, and animal sources. In an embodiment,the unsaturated ester oil comprises a triglyceride derived fromgenetically modified nuts, vegetables, plant, and animal sources.

In an aspect, the unsaturated natural source oil can be tallow, olive,peanut, castor bean, sunflower, sesame, poppy, seed, palm, almond seed,hazel-nut, rapeseed, canola, soybean, corn, safflower, canola,cottonseed, camelina, flaxseed, or walnut oil. In some embodiment, theunsaturated natural source oil can be soybean, corn, castor bean,safflower, canola, cottonseed, camelina, flaxseed, or walnut oil. Infurther embodiments, the unsaturated natural source oil can be soybeanoil; alternatively corn oil; alternatively castor bean oil; oralternatively, canola oil.

The unsaturated natural source oils are comprised of triglycerides thatcan be described as an ester of glycerol and an unsaturated carboxylicacid. Within this description, the unsaturated carboxylic acid portionof the triglyceride can be called a glycerol side chain (or more simplya side chain). In some embodiments, the triglyceride comprises less than30 percent of side chains comprising methylene interrupted double bonds.In other embodiments, embodiments the triglyceride comprises greaterthan 30 percent of the side chains comprise methylene interrupted doublebonds. In yet other embodiments, the triglyceride comprises less than 25percent of side chains having 3 contiguous methylene interruptedcarbon-carbon double bonds. In further embodiments, the triglyceridecomprises less than 25 percent linolenic acid side chains. In furtherembodiments, the triglyceride comprises greater than 25 percent of sidechains having 3 contiguous methylene interrupted carbon-carbon doublebonds. In further embodiments, the triglyceride comprises greater than25 percent linolenic acid side chains. In additional embodiments, thetriglyceride comprises at least 30 percent side chains having 2contiguous methylene interrupted carbon-carbon double bonds and lessthan 25 percent of side chains having 3 contiguous methylene interruptedcarbon-carbon double bonds.

In another embodiment, the unsaturated natural ester oil comprises“natural” triglycerides derived from unsaturated natural source oils. Inan embodiment, the unsaturated ester oil is synthetic. In an embodiment,the unsaturated ester oil comprises both synthetic and natural rawmaterials. In an embodiment, the unsaturated ester oil comprisessynthetic triglycerides.

Synthetic Unsaturated Esters

Synthetic unsaturated esters used as feedstock for aspects of thisinvention can be produced using methods for producing an ester groupknown to those skilled in the art. The term “ester group” means a moietyformed from the reaction of a hydroxy group and a carboxylic acid or acarboxylic acid derivative. Typically, the esters can be produced byreacting an alcohol with a carboxylic acid, transesterification ofcarboxylic acid ester with an alcohol, reacting an alcohol with acarboxylic acid anhydride, or reacting an alcohol with a carboxylic acidhalide. Any of these methods can be used to produce the syntheticunsaturated ester oils used as a feedstock in an aspect of thisinvention. The alcohol, unsaturated carboxylic acid, unsaturatedcarboxylic acid ester, unsaturated carboxylic acid anhydride rawmaterials for the production of the unsaturated ester oil can be derivedfrom natural, synthetic, genetic, or any combination of natural,genetic, and synthetic sources.

The polyols and the unsaturated carboxylic acids, simple unsaturatedcarboxylic acid esters, or unsaturated carboxylic acid anhydrides usedto produce the unsaturated esters used as a feedstock in various aspectsof this invention are independent elements. That is, these elements canbe varied independently of each other and thus, can be used in anycombination to produce an unsaturated ester utilized a feedstock toproduce the compositions described in this application or as a feedstockfor the processes described in this application.

Synthetic Unsaturated Ester Oils—Polyol Component

The polyol used to produce the unsaturated ester oil can be any polyolor mixture of polyols capable of reacting with an unsaturated carboxylicacid, unsaturated simple carboxylic acid ester, carboxylic acidanhydride, or carboxylic acid halide under reaction condition known tothose skilled in the art.

The number of carbon atoms in the polyol is not particularly important.In one aspect, the polyol used to produce the unsaturated ester cancomprise from 2 to 20 carbon atoms. In other embodiments, the polyolcomprises from 2 to 10 carbon atoms; alternatively from 2 to 7 carbonatoms; alternatively from 2 to 5 carbon atoms. In further embodiments,the polyol may be a mixture of polyols having an average of 2 to 20carbon atoms; alternatively, an average of from 2 to 10 carbon atoms;alternatively, an average of 2 to 7 carbon atoms; alternatively anaverage of 2 to 5 carbon atoms.

In another aspect, the polyol used to produce the unsaturated ester canhave any number of hydroxy groups needed to produce the unsaturatedester as described herein. In some embodiments, the polyol has 2 hydroxygroups; alternatively 3 hydroxy groups; alternatively, 4 hydroxy groups;alternatively, 5 hydroxy groups; or alternatively, 6 hydroxy groups. Inother embodiments, the polyol comprises at least 2 hydroxy groups;alternatively at least 3 hydroxy groups; alternatively, at least 4hydroxy groups; or alternatively, at least 5 hydroxy groups; at least 6hydroxy groups. In yet other embodiments, the polyol comprises from 2 to8 hydroxy groups; alternatively, from 2 to 4 hydroxy groups; oralternatively from 4 to 8 hydroxy groups.

In further aspects, the polyol used to produce the unsaturated ester isa mixture of polyols. In an embodiment, the mixture of polyols has anaverage of at least 1.5 hydroxy groups per polyol molecule. In otherembodiments, the mixture of polyols has an average of at least 2 hydroxygroups per polyol molecule; alternatively, an average of at least 2.5hydroxy groups per polyol molecule; alternatively, an average of atleast 3.0 hydroxy groups per polyol molecule; or alternatively, anaverage of at least 4 hydroxy groups per polyol molecule. In yet anotherembodiments, the mixture of polyols has an average of 1.5 to 8 hydroxygroups per polyol molecule; alternatively, an average of 2 to 6 hydroxygroups per polyol molecule; alternatively, an average of 2.5 to 5hydroxy groups per polyol molecule; alternatively, an average of 3 to 4hydroxy groups per polyol molecule; alternatively, an average of 2.5 to3.5 hydroxy groups per polyol molecule; or alternatively, an average of2.5 to 4.5 hydroxy groups per polyol molecule.

In yet another aspect, the polyol or mixture of polyols used to producethe unsaturated thiol ester has a molecular weight or average molecularweight less than 500. In other embodiments, the polyol or mixture ofpolyols have a molecular weight or average molecular weight less than300; alternatively less than 200; alternatively, less than 150; oralternatively, less than 100.

In some embodiments, suitable polyols include 1,2-ethanediol,1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,dimethylolpropane, neopentylpropane, 2-propyl-2-ethyl-1,3-propanediol,1,2-propanediol, 1,3-butanediol, diethylene glycol, triethylene glycol,polyethylene glycol, dipropylene glycol, tripropylene glycol, andpolypropylene glycol; cyclohexanedimethanol, 1,3-dioxane-5,5-dimethanol;and 1,4-xylylenedimethanol and 1-phenyl-1,2-ethanediol,trimethylolpropane, trimethylolethane, trimethylolbutane, glycerol,1,2,5-hexanetriol, pentaerythritol, ditrimethylolpropane, diglycerol,ditrimethylolethane, 1,3,5-trihydroxybenzene, 1,4-xylylenedimethanol,and 1-phenyl-1,2-ethanediol, or any combination thereof. In furtherembodiments, the polyol is glycerol, pentaerythritol, or mixturesthereof. In other embodiments, the polyol is glycerol, or alternativelypentaerythritol.

Synthetic Unsaturated Ester—Carboxylic Acid or Carboxylic AcidEquivalent Component

The carboxylic acid component of the unsaturated ester oil can be anycarboxylic acid or mixture of carboxylic acids comprising acarbon-carbon double bond. As the carboxylic acid component will becombined with a polyol or polyol mixture comprising an average ofgreater than 1.5 hydroxy groups or any other number of hydroxy groupsdescribed herein, the carboxylic acid component can be any mixturecomprising unsaturated carboxylic acids that produces an unsaturatedester oil meeting the feedstock requirement described herein. In someembodiments, the carboxylic acid component can be any mixture ofsaturated carboxylic acids and unsaturated carboxylic acid that producesan unsaturated ester oil meeting the feedstock requirement describedherein. Thus, the carboxylic acid or carboxylic acid mixture used toproduce the synthetic unsaturated ester oil can be described as havingan average number of a specified element per carboxylic acid.

Independent elements of the carboxylic acid include the average numberof carboxylic acid groups per carboxylic acid molecule, the averagenumber of carbon atoms present in the carboxylic acid, and the averagenumber of carbon-carbon double bonds per carboxylic acid. Additionalindependent elements include the position of the double bond in thecarbon chain and the relative position of the double bonds in respect toeach other when there are multiple double bonds.

Specific carboxylic acids used as a component of the carboxylic acidcomposition used to produce the unsaturated ester oil can have from 3 to30 carbon atoms per carboxylic acid molecule. In some embodiments thecarboxylic acid is linear. In some embodiments the carboxylic acid isbranched. In some embodiments the carboxylic acid is a mixture of linearand branched carboxylic acids. In some embodiments the carboxylic acidcan also comprise additional functional groups including alcohols,aldehydes, ketones, and epoxides, among others.

Suitable carboxylic acids that can be used as a component of unsaturatedcarboxylic acid composition can have from about 3 to about 30 carbonatoms; alternatively 8 to 25 carbon atoms; or alternatively, from 12 to20 carbon atoms. In other embodiments, the carboxylic acids comprisingthe unsaturated carboxylic acid composition comprise an average of 2 to30 carbon atoms; alternatively an average of 8 to 25 carbon atoms; oralternatively, and average of from 12 to 20 carbon atoms.

The carbon-carbon double bond can be located anywhere along the lengthof the carbon-carbon chain. In one embodiment, the double bond can belocated at a terminal position. In another embodiment, the carbon-carbondouble bond can be located at internal position. In yet anotherembodiment, the carboxylic acid or mixture of carboxylic acids cancomprise both terminal and internal carbon-carbon double bonds. Thedouble bond can also be described by indicating the number ofsubstitutes that are attached to carbon-carbon double bond. In someembodiments, the carbon-carbon double bond can be mono-substituted,disubstituted, trisubstituted, tetrasubstituted, or a mixture ofunsaturated carboxylic acids that can have any combination ofmonosubstituted, disubstituted, trisubstituted and tetrasubstitutedcarbon-carbon double bonds.

Suitable unsaturated carboxylic acid include acrylic, agonandoic,agonandric, alchornoic, ambrettolic, angelic, asclepic, auricolic,avenoleic, axillarenic, brassidic, caproleic, cetelaidic, cetoleic,civetic, CLA, coriolic, coronaric, crepenynic, densipolic,dihomolinoleic, dihomotaxoleic, dimorphecolic, elaidic, ephedrenic,erucic, gadelaidic, gadoleic, gaidic, gondolo, gondoleic, gorlic,helenynolic, hydrosorbic, isoricinoleic, keteleeronic, labellenic,lauroleic, lesquerolic, linelaidic, linderic, linoleic, lumequic,malvalic, mangold's acid, margarolic, megatomic, mikusch's acid,mycolipenic, myristelaidic, nervoic, obtusilic, oleic, palmitelaidic,petroselaidic, petroselinic, phlomic, physeteric, phytenoic, pyrulic,ricinelaidic, rumenic, selacholeic, sorbic, stearolic, sterculic,sterculynic, stillingic, strophanthus, tariric, taxoleic, traumatic,tsuduic, tsuzuic, undecylenic, vaccenic, vemolic, ximenic, ximenynic,ximenynolic, and combinations thereof. In further embodiments, suitableunsaturated carboxylic acids include oleic, palmitoleic, ricinoleic,linoleic, and combination thereof.

In some embodiments the unsaturated ester can be produced bytransesterification of a simple ester of the carboxylic acid or mixtureof carboxylic acids described herein with the polyol compositionsdescribed herein. In some embodiment, the simple ester, is a methyl orethyl ester of the carboxylic acid or mixture of carboxylic acids. Infurther embodiments the simple carboxylic acid ester is a methyl esterof the carboxylic acids as described herein.

Epoxidized Unsaturated Esters

In an aspect, epoxidized unsaturated esters are used as a feedstock toproduce materials described herein and for the process to produce thematerial described herein. Generally, the epoxidized unsaturated estercan be derived by epoxidizing any unsaturated ester described herein.The unsaturated ester oil can be derived from natural sources,synthetically produced from natural source raw materials, produced fromsynthetic raw materials, produced from a mixture of natural andsynthetic materials, or a combination thereof.

Minimally, the epoxidized unsaturated ester comprises at least oneepoxide group. In an embodiment the epoxidized unsaturated estercomprises at least 2 epoxide groups; alternatively, at least 3 epoxidegroups; or alternatively, at least 4 epoxide. In other embodiments, theepoxidized unsaturated ester comprises from 2 to 9 epoxide groups;alternatively, from 2 to 4 epoxide groups; alternatively, from 3 to 8epoxide groups; or alternatively, from 4 to 8 epoxide groups.

In some embodiments, the unsaturated ester comprises a mixture ofepoxidized unsaturated esters. In this aspect, the number of epoxidegroups in the epoxidized unsaturated ester is best described as anaverage number of epoxide groups per epoxidized unsaturated estermolecule. In some embodiments, the epoxidized unsaturated esters have anaverage of at least 1.5 epoxide groups per epoxidized unsaturated estermolecule; alternatively, an average of at least 2 epoxide groups perepoxidized unsaturated ester molecule; alternatively, an average of atleast 2.5 epoxide groups per epoxidized unsaturated ester molecule; oralternatively, an average of at least 3 epoxide groups per epoxidizedunsaturated ester molecule. In other embodiments, the epoxidizedunsaturated esters have average of from 1.5 to 9 epoxide groups perepoxidized unsaturated ester molecule; alternatively, an average of from3 to 8 epoxide groups per epoxidized unsaturated ester molecule;alternatively, an average of from 2 to 4 epoxide groups per epoxidizedunsaturated ester molecule; or alternatively, from of 4 to 8 epoxidegroup per epoxidized unsaturated ester molecule.

In an aspect the epoxidized unsaturated ester can be an epoxidizedunsaturated natural source oil (epoxidized natural source oil). Theunsaturated natural source oil can be derived from naturally occurringnut, vegetable, plant and animal sources. In an embodiment, theunsaturated ester oil is derived from genetically modified nuts,vegetables, plant, and animal sources. In an embodiment, the unsaturatedester oil comprises a triglyceride derived from genetically modifiednuts, vegetables, plant, and animal sources.

In an aspect, the epoxidized natural source oil can be tallow, olive,peanut, castor bean, sunflower, sesame, poppy, seed, palm, almond seed,hazel-nut, rapeseed, canola, soybean, corn, safflower, canola,cottonseed, camelina, flaxseed, or walnut oil. In some embodiment, theepoxidized natural source oil can be soybean, corn, castor bean,safflower, canola, cottonseed, camelina, flaxseed, or walnut oil. Infurther embodiments, the epoxidized natural source oil can be soybeanoil; alternatively corn oil; alternatively castor bean oil; oralternatively, canola oil.

The thiol composition can include an average of greater than 0 to about4 epoxide groups per triglyceride. The thiol composition can alsoinclude an average of greater than 1.5 to about 9 epoxide groups pertriglyceride.

Mercaptans

Within some embodiments, an unsaturated ester or an epoxidizedunsaturated ester is contacted with mercaptan. Within these embodiments,the mercaptan can be any mercaptan comprising from 1 to 20 carbon atoms.Generally, the mercaptan can have the following structure:HS—R³wherein R3 is a C1 to C20 organyl groups or a C1 to C20 hydrocarbylgroups. In further embodiments the R3 can be a C2 to C10 organyl groupor a C2 to C10 hydrocarbyl group. In some embodiments, the mercaptancomposition comprises a solvent. In one aspect, the mercaptancomposition comprises at least one other functional group.

The at least one other functional group can be selected from severaldifferent groups. For example, the at least one other functional groupis an alcohol group, a carboxylic alcohol group, a carboxylic estergroup, an amine group, a sulfide group, a thiol group, a methyl or ethylester of a carboxylic acid group, or combinations thereof. Other typesof functional groups will be apparent to those of skill in the art andare to be considered within the scope of the present invention.

In some embodiments, the mercaptan is selected from the group consistingof 3-mercaptopropyl-trimethoxysilane, 2-mercaptopyridine,4-mercaptopyridine, 2-mercaptopyrimidine, mercaptopyruvic acid,mercaptosuccinic acid, 2-mercaptonicotinic acid, 6-mercaptonicotinicacid, 2-mercaptophenol, 4-mercaptophenol, 3-mercapto-1,2-propanediol,3-mercapto-1,2-propanediol, 3-mercapto-1-propanesulfonic acid,1-mercapto-2-propanol, 3-mercapto-1-propanol, 2-mercaptopropionic acid,3-mercaptopropionic acid, 2-mercaptobenzyl alcohol,3-mercapto-2-butanol, 4-mercapto-1-butanol, 2-mercaptoethanesulfonicacid, 2-mercaptoethanol, 2-mercaptoethyl ether, 2-mercaptoethyl sulfide,16-mercaptohexadecanoic acid, 6-mercapto-1-hexanol,4′-mercaptoacetanilide, mercaptoacetic acid, 2-mercaptobenzoic acid,3-mercaptobenzoic acid, 4-mercaptobenzoic acid, 2-mercaptothiazoline,3-mercapto-1H-1,2,4-triazole, 11-mercaptoundecanoic acid,11-mercapto-1-undecanol, or combinations thereof.

In some embodiments, the mercaptan is selected from the group consistingof beta-mercaptoethanol, 2-mercaptophenol, 3-mercaptophenol,4-mercaptophenol, 1-mercapto-2-propanol, 1-mercapto-3-propanol,mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid,2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptobenzoic acid,2-mercaptobenzylalcohol, 3-mercapto-2-butanol, 4-mercapto-1-butanol,2-mercaptoethyl ether, 2-mercaptoethyl sulfide, 6-mercapto-hexanol,3-mercapto-1,2-propanediol, mercaptosuccinic acid, and mixtures thereof.In further embodiments, the mercaptan is selected from the groupconsisting of beta-mercaptoethanol, 1-mercapto-2-propanol,1-mercapto-3-propanol, 2-mercaptobenzylalcohol, 3-mercapto-2-butanol,4-mercapto-1-butanol, 6-mercapto-hexanol, 3-mercapto-1,2-propanediol,and mixtures thereof. In further embodiments, the mercaptan is selectedfrom the group consisting 2-mercaptophenol, 3-mercaptophenol,4-mercaptophenol, and mixtures thereof. In yet further embodiments, themercaptan is selected from the group consisting mercaptoacetic acid,2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptobenzoicacid, 3-mercaptobenzoic acid, 4-mercaptobenzoic acid, mercaptosuccinicacid, and mixtures thereof.

Isocyanates

Within some embodiments, the inventive compositions described herein arereacted with an isocyanate compound to produce a polythiourethanecomposition. The isocyanate may be any isocyanates capable of reactingwith the thiol esters, hydroxy thiol esters, and a cross-linked thiolesters described herein to form a polyurethane composition. Generally,the isocyanate compound has at least two isocyanate groups.

In an aspect the isocyanates can be selected from the group consistingof 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate,2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylenediisocyanate, cyclohexane-1,3- and -1,4-diisocyanate,1-isocyanato-2-isocyanatomethyl cyclopentane,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophoronediisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)-methane, 1,3- and1,4-bis-(isocyanatomethyl)-cyclohexane,bis-(4-isocyanatocyclo-hexyl)-methane, 2,4′-diisocyanato-dicyclohexylmethane, bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,(.alpha.,.alpha.,.alpha.′,.alpha.′-tetramethyl-1,3- and/or -1,4-xylylenediisocyanate, 1-isocyanato-1-methyl-4(3)-isocyanatomethyl cyclohexane,2,4- and/or 2,6-hexahydro-toluylene diisocyanate, 1,3- and/or1,4-phenylene diisocyanate, 2,4- and/or 2,6-toluylene diisocyanate, 2,4-and/or 4,4′-diphenylmethane diisocyanate and 1,5-diisocyanatonaphthalene and mixtures thereof. In some embodiments, the isocyanatecompound is selected from the group consisting ofbis-(4-isocyanatocyclohexyl)-methane, 1,6-hexamethylene diisocyanate,isophorone diisocyanate,.alpha.,.alpha.,.alpha.′,.alpha.′-tetramethyl-1,3- and/or -1,4-xylylenediisocyanate, 2,4- and/or 2,6-toluylene diisocyanate, and 2,4- and/or4,4′-diphenylmethane diisocyanate. In other embodiments, the isocyanatecompound is selected from the group consisting of isophoronediisocyanate, 2,4-toluylene diisocyanate and mixtures of 2,4- and2,6-toluylene diisocyanate. In yet further embodiments, the isocyanatecompound can be 4,4′-methylenebis(phenyl) diisocyanate (MDI),4,4′-methylenebis(cyclohexyl) diisocyanate (Hydrogenated MDI), tolylene2,4-diisocyanate (TDI), 1,6-diisocyanatohexane (HDI), and Luprinate™M20S.

EXAMPLES

Mercaptanized Soybean Oil

Soybean oil was reacted with hydrogen sulfide in the presence of aninitiator to produce mercaptanized soybean oil in accordance with themethod steps described herein. Several examples follow utilizing thesame procedure.

In the examples that included reacting soybean oil with hydrogen sulfidein the presence of UV light, the following feedstocks were utilized:Refined (Food Grade) Soybean Oil (Cargill); Unrefined Non-degummedSoybean Oil (ADM Supplier); Hydrogen Sulfide (Tessenderlo Sourcing, AirProducts >99.9% Purity); and Tri-n-butylphosphite (Aldrich, 90%).

In order to quantitatively measure the thiol sulfur, the thiol sulfuranalyses were conducted using silver nitrate titration in accordancewith ASTM D3227, with the following modifications designed to minimizeprobe fouling by silver salts: the samples were diluted in a known massof tetrahydrofuran. The silver nitrate concentration was 0.01 Nstandardized against potassium iodide.

Example 1

The soybean oil (see sourcing above, 500 mL) was charged to a 5 literstainless steel autoclave reactor fitted with a horizontal quartz tubecontaining a 100 Watt Hanovia Medium Pressure UV lamp. The system wasflushed with nitrogen and sealed at ambient pressure. Liquid hydrogensulfide (1.96 kg) was charged to the reactor. The reactor pressure was307 psig. Excess heat was dissipated by means of a circulating bathoperating at 18° C. The reactor agitator was started. The lamp wasswitched on for a period of 30 minutes. The reactor was slowlydepressurized to a high-pressure flare line through a top portal vent.The product was then sparged with nitrogen to the high-pressure flare.The crude mercaptanized soybean oil was then drained out through abottom drain valve.

The resulting mercaptanized soybean oil was subjected to nitrogensparging under reduced pressure at 100° C. for a period of 4 hours toremove any residual hydrogen sulfide.

Thiol sulfur was analyzed by three different tests. The first test usedwas the modified ASTM D3227, which resulted in a thiol sulfurmeasurement of 4.64%. The second test used to measure the thiol sulfurwas SLP-1204, which is a test developed by Chevron Phillips ChemicalCompany LLP. By using the SLP-1204 test, the resulting thiol sulfurmeasurement was 4.28%. Lastly, the total sulfur was measured bycombustion analysis, which resulted in a total sulfur measurement of4.27%.

Example 2

Vegetable oil (42 kg) was charged to a 100-gallon holding vessel. Thevessel was purged with nitrogen and returned to atmospheric pressure.Hydrogen sulfide (174 kg) was charged to the holding vessel. The vesseltemperature was controlled from 25-30° C. while the pressure wastypically maintained between 380-400 psig. The reactants werecontinuously rolled from the holding tank through a stainless steeltubular photochemical reactor containing a 7.5 KW Hanovia mediumpressure mercury lamp contained within a quartz tube. Reactortemperature, pressure, and composition were monitored over the course ofthe reaction. The reaction time was dependent upon reaching a desiredcomposition of thiol sulfur. Upon completion, the unreacted hydrogensulfide was slowly vented from the system. Residual H₂S was removed at100° C. and reduced pressure while passing nitrogen through a nitrogensparge tube. The product was drained from the bottom of the reactor intoa clean drum. The thiol sulfur measurements were 11.0% when using themodified ASTM D3227, 8.74% when using SLP-1204, and the total sulfur was11.21% when using combustion analysis (total sulfur).

Example 3

The soybean oil (see sourcing above, 180 mL) and tri-n-butylphosphite(1.8 mL) was charged to a 1.5 liter stainless steel autoclave reactorfitted with a horizontal quartz tube containing a 100 Watt HanoviaMedium Pressure UV lamp. The system was flushed with nitrogen and sealedat ambient pressure. Liquid hydrogen sulfide (1.96 kg) was charged tothe reactor. The reactor pressure was 307 psig. The circulating bath wasstarted and bath temperature set at 18° C. The reactor agitator wasstarted. The lamp was switched on for a period of 30 minutes. Thereactor was slowly depressurized to a high-pressure flare line through atop portal vent. The reactor product was then sparged with nitrogen tothe high-pressure flare. The crude mercaptanized soybean oil was thendrained out through a bottom drain valve.

The resulting mercaptanized soybean oil was subjected to nitrogensparging under reduced pressure at 100° C. for a period of 4 hours toremove any residual hydrogen sulfide. The thiol sulfur measurements were13.0% when using the modified ASTM D3227, 9.82% when using SLP-1204, and11.69% when using combustion analysis.

Table 1 provides the properties of the mercaptanized soybean oilproduced in examples 1-3.

TABLE 1 Mercaptanized Soybean Oil Product Properties Cyclic Sulfide toC═C to Thiol Sulfur^(†) Thiol Group Thiol groups Example (wt %) MolarRatio Molar Ratio 1 4.28 0.02 2.79 2 11.0 0.03 0.26 3 13.0 0.03 0.51^(†)Thiol sulfur content determined by the modified ASTM D3227

Samples of modified soybean oil and modified linseed oil were alsosubjected to methanolysis substantially according to the proceduredescribed in U.S. Pat. No. 3,991,089, which is incorporated herein byreference. 1 gram of mercaptanized soybean oil was placed in a roundbottom flask. A solution of sodium methoxide in methanol (25%, 2.0 mL)was added to the mercaptanized oil and the mixture was stirred for about1 hour at room temperature. Toluene (10 mL) and distilled water (5 mL)were added. The mixture was acidified with 0.5 N HCl until a pH of about2-3 was obtained. The resulting layers were separated and the top layerwas dried over MgSO₄ prior to filtering. The resulting samples wereanalyzed by GC-MS.

Example 4

Soybean oil was reacted with hydrogen sulfide in a 1000 gallon reactorhaving six medium pressure ultraviolet 7500 watt UV lamps. The generalprocedure for five mercaptanized soybean production runs is providedbelow.

Soybean oil was charged to a 1000 gallon stirred reactor. Hydrogensulfide was then charged to the reactor. After the hydrogen sulfide wascharged to the reactor, the stirrers and the UV lamps were turned on andthe reaction allowed to build temperature and pressure as the reactionproceed. The reaction was continued until a minimum thiol sulfur contentof 8 weight percent was achieved. After reaction was completion, theexcess hydrogen sulfide was flashed from the reactor. For runs 2-5, themercaptanized soybean oil product underwent an additional hydrogensulfide stripping step comprising stripping hydrogen sulfide from theproduct under vacuum, 50 mm Hg, at 250° F. (only true for runs 2-5).

Table 2 provides the soybean oil and hydrogen sulfide charges to thereactor for five 1000 gallon reactor runs. The Table 2 also provides theapproximate carbon-carbon double bond to hydrogen sulfide ratio basedupon an average of 4.5 carbon-carbon double bonds per soybean oilmolecule. Additionally, Table 2 provides the temperature and pressureranges of the reactor during the reaction of soybean oil with hydrogensulfide.

TABLE 2 1000 gallon reactor Mercaptanized Soybean Oil Production RunConditions Soybean Hydrogen Run oil Sulfide C═C to H₂S Time TemperaturePressure Number (lbs) (lbs) Molar Ratio (hours) (° C.) (psig) 1 22644526 12 35 29-41 295-384 2 971 6039 38 10 31-44 323-429 3 513 6500 78<5.1 29-48 309-449 4 524 6528 77 3 26-43 279-424 5 276 6648 148 2 40-43241-355

Table 3 provides the details of the analysis of the mercaptanizedsoybean oil producing in the five 1000 gallon reactor runs.

TABLE 3 1000 gallon reactor Mercaptanized Soybean Oil Product PropertiesSide Chain Cyclic Sulfide to C═C to Thiol Containing Run ThiolSulfur^(†) Thiol Group groups Thiol Groups Number (wt %) Molar RatioMolar Ratio (%) 1 9.3 — — 71.6 2 9.6 0.04 0.48 72.3 3 9.2 0.03 0.59 69.14 9.3 0.03 0.62 71.6 5 10.1 0.03 0.54 72.3 ^(†)Thiol sulfur contentdetermined by Raman spectroscopyMercaptanized Castor Bean Oil

Castor oil was reacted with hydrogen sulfide in the presence of aninitiator to produce mercaptanized castor bean oil in accordance withthe method steps described herein. Several examples follow utilizing thesame procedure. In the examples that included reacting castor bean oilwith hydrogen sulfide the following feedstocks were utilized: Castor Oil(Aldrich); Hydrogen Sulfide (Tessenderlo Sourcing, Air Products >99.9%Purity); and Tri-n-butylphosphite (Aldrich, 90%).

Example 1

Castor oil, 140 mL was charged to a 1.5 liter stainless steel autoclavereactor fitted with a horizontal quartz tube containing a 100 WattHanovia Medium Pressure UV lamp. The system was flushed with nitrogenand sealed at ambient pressure. Liquid hydrogen sulfide (0.76 kg) wascharged to the reactor. The reactor pressure was 419 psig. The reactoragitator was started and adjusted to 800 rpm. The lamp was switched onfor a period of 2 hours. The reaction temperature varied from 33.9 to40.8° C. The final reactor pressure was 448 psig. The lamp was switchedoff and the reactor was slowly depressurized to a high-pressure flareline through a top portal vent. The reactor product was then spargedwith nitrogen to the high-pressure flare. The crude mercaptanizedsoybean oil was then drained out through a bottom drain valve.

Example 2

Castor oil (140 mL) and tri-n-butylphosphite (1.4 mL) was charged to a1.5 liter stainless steel autoclave reactor fitted with a horizontalquartz tube containing a 100 Watt Hanovia Medium Pressure UV lamp. Thesystem was flushed with nitrogen and sealed at ambient pressure. Liquidhydrogen sulfide (0.76 kg) was charged to the reactor. The reactorpressure was 418 psig. The reactor agitator was started and adjusted to800 rpm. The lamp was switched on for a period of 4 hours. The reactiontemperature varied from 33.2 to 40.9° C. The final reactor pressure was456 psig. The lamp was switched off and the reactor was slowlydepressurized to a high-pressure flare line through a top portal vent.The reactor product was then sparged with nitrogen to the high-pressureflare. The crude mercaptanized soybean oil was then drained out througha bottom drain valve.

The analytical properties of the two mercaptanized castor oil productsare provide in Table 4.

TABLE 4 Mercaptanized Castor Oil Product Properties Thiol C═C to SideChain Sulfur^(†) Thiol groups Containing Thiol Example (wt %) MolarRatio Groups (%) 1 6.4 0.52 64.1 2 7.4 0.26 77.7 ^(†)Thiol sulfurcontent determined by Raman spectroscopyMercaptohydroxy Soybean Oil Synthetic Procedure

Example 1 CPC407-81D

Epoxidized Soybean Oil (700 g, ˜0.7 mol) and1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 4.7 g, 30.5 mmol) were chargedto a 1-L Hastelloy C autoclave reactor that was pressure tested to 630psig. Hydrogen sulfide (H₂S, 132.0 g, 3.87 mol) was then pressured intothe stirred reactor contents through a dip tube in the liquid space. Thereaction mixture was heated and maintained at 85° C. with stirring for 8hrs, during which time the reactor pressure decreased from a maximum of351 psig to 219 psig. The stirrer was stopped and while still warm(80-85° C.), excess H₂S was slowly vented to a low-pressure flare. Thereactor vapor space was then swept with N₂ for 1 hr and the reactorcontents drained warm (80-85° C.). The reaction product was N₂ spargedunder vacuum (<5 mmHg) at 130-140° C. for 16 hrs to remove residual H₂S.The resulting light yellow, viscous sticky oil had a thiol sulfur(titration by modified ASTM D3227) content of 7.53 wt. %, 2.5SH/molecule, or 2.35 meq SH/g. Combustion analysis indicated C, 64.37%,H, 10.20%, N, <0.15%, and S, 9.51%.

Example 2 CPC407-83

Epoxidized Soybean Oil (600 g, ˜0.6 mol) and1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 5.0 g, 32.4 mmol) were chargedto a 1-L Hastelloy C autoclave reactor, and the vessel was pressuretested to 630 psig. Hydrogen sulfide (H₂S, 204.0 g, 5.99 mol) was thenpressured into the stirred reactor contents through a dip tube in theliquid space. The reaction mixture was heated and maintained at 97° C.with stirring for 14 hrs, during which time the reactor pressuredecreased from a maximum of 509 psig to 229 psig. The stirrer wasstopped and while still warm (90-95° C.), excess H₂S was slowly ventedto a low-pressure flare. The reactor vapor space was then swept with N₂for 1 hr and the reactor contents drained warm (80-85° C.). The reactionproduct was N₂ sparged under vacuum (<50 mmHg) at 130-140° C. for 16 hrsto remove residual H₂S. The resulting light yellow, viscous sticky oilhad a thiol sulfur (titration by modified ASTM D3227) content of 4.14wt. %, 1.4 SH/molecule, or 1.29 meq SH/g. Combustion analysis indicatedC, 65.18%, H, 10.17%, N, <0.15%, and S, 7.80%.

Example 3 CPC407-86

Epoxidized Soybean Oil (600 g, ˜0.6 mol) and1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 5.0 g, 32.4 mmol) were chargedto a 1-L Hastelloy C autoclave reactor, and the vessel was pressuretested to 630 psig. Hydrogen sulfide (H₂S, 204.0 g, 5.99 mol) was thenpressured into the stirred reactor contents through a dip tube in theliquid space. The reaction mixture was heated and maintained at 85° C.with stirring for 10 hrs, during which time the reactor pressuredecreased from a maximum of 578 psig to 489 psig. The stirrer wasstopped and while still warm (80-85° C.), excess H₂S was slowly ventedto a low-pressure flare. The reactor vapor space was then swept with N₂for 1 hr and the reactor contents drained warm (80-85° C.). The reactionproduct was N₂ sparged under vacuum (<50 mmHg) at 130-140° C. for 16 hrsto remove residual H₂S. The resulting light yellow, viscous sticky oilhad a thiol sulfur (titration with modified ASTM D3227) content of 8.28wt. %, 2.8 SH/molecule, or 2.58 meq SH/g. Combustion analysis indicatedC, 65.24%, H, 9.52%, N, 0.18%, and S, 9.53%.

Example 4 CPC407-88

Epoxidized soybean oil (600 g, ˜0.6 mol) and1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 5.0 g, 32.4 mmol) were chargedto a 1-L Hastelloy C autoclave reactor that was pressure tested to 630psig. Hydrogen sulfide (H₂S, 204.0 g, 5.99 mol) was then pressured intothe stirred reactor contents through a dip tube in the liquid space. Thereaction mixture was heated and maintained at 85° C. with stirring for12 hrs, during which time the reactor pressure decreased from a maximumof 587 psig to 498 psig. The stirrer was stopped and while still warm(80-85° C.), excess H₂S was slowly vented to a low-pressure flare. Thereactor vapor space was then swept with N₂ for 1 hr and the reactorcontents drained warm (80-85° C.). The reaction product was N₂ spargedunder vacuum (<50 mmHg) at 130-140° C. for 16 hrs to remove residualH₂S. The resulting light yellow, viscous sticky oil had a thiol sulfur(titration by modified ASTM D3227) content of 8.24 wt. %, 2.8SH/molecule, or 2.57 meq SH/g. Combustion analysis indicated C, 63.39%,H, 10.01%, N, <0.15%, and S, 8.76%.

Example 5 CPC407-93

Epoxidized soybean oil (600 g, ˜0.6 mol) and1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 5.0 g, 32.4 mmol) were chargedto a 1-L Hastelloy C autoclave reactor, and the vessel was pressuretested to 630 psig. Hydrogen sulfide (H₂S, 204.0 g, 5.99 mol) was thenpressured into the stirred reactor contents through a dip tube in theliquid space. The reaction mixture was heated and maintained at 85° C.with stirring for 8 hrs, during which time the reactor pressuredecreased from a maximum of 606 psig to 537 psig. The stirrer wasstopped and while still warm (80-85° C.), excess H₂S was slowly ventedto a low-pressure flare. The reactor vapor space was then swept with N₂for 1 hr and the reactor contents drained warm (80-85° C.). The reactionproduct was N₂ sparged under vacuum (<50 mmHg) at 130-140° C. for 16 hrsto remove residual H₂S. The resulting light yellow, viscous sticky oilhad a thiol sulfur (titration by modified ASTM D3227) content of 7.34wt. %, 2.5 SH/molecule, or 2.29 meq SH/g. Combustion analysis indicatedC, 64.47%, H, 10.18%, N, <0.15%, and S, 8.40%.

Example 6 CPC407-94

Epoxidized soybean oil (600 g, ˜0.6 mol) and1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 5.0 g, 32.4 mmol) were chargedto a 1-L Hastelloy C autoclave reactor that was pressure tested to 630psig. Hydrogen sulfide (H₂S, 204.0 g, 5.99 mol) was then pressured intothe stirred reactor contents through a dip tube in the liquid space. Thereaction mixture was heated and maintained at 85° C. with stirring for 6hrs, during which time the reactor pressure decreased from a maximum of586 psig to 556 psig. The stirrer was stopped and while still warm(80-85° C.), excess H₂S was slowly vented to a low-pressure flare. Thereactor vapor space was then swept with N₂ for 1 hr and the reactorcontents drained warm (80-85° C.). The reaction product was N₂ spargedunder vacuum (<50 mmHg) at 130-140° C. for 16 hrs to remove residualH₂S. The resulting light yellow, viscous sticky oil had a thiol sulfur(titration by modified ASTM D3227) content of 5.93 wt. %, 2.0SH/molecule, or 1.85 meq SH/g. Combustion analysis indicated C, 65.26%,H, 10.19%, N, <0.15%, and S, 8.43%.

Example 7 CPC407-95

Epoxidized soybean oil (600 g, ˜0.6 mol) and1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 5.0 g, 32.4 mmol) were chargedto a 1-L Hastelloy C autoclave reactor, and the vessel was pressuretested to 630 psig. Hydrogen sulfide (H₂S, 204.0 g, 5.99 mol) was thenpressured into the stirred reactor contents through a dip tube in theliquid space. The reaction mixture was heated and maintained at 85° C.with stirring for 4 hrs, during which time the reactor pressuredecreased from a maximum of 595 psig to 554 psig. The stirrer wasstopped and while still warm (80-85° C.), excess H₂S was slowly ventedto a low-pressure flare. The reactor vapor space was then swept with N₂for 1 hr and the reactor contents drained warm (80-85° C.). The reactionproduct was N₂ sparged under vacuum (<50 mmHg) at 130-140° C. for 16 hrsto remove residual H₂S. The resulting light yellow, viscous sticky oilhad a thiol sulfur (titration by modified ASTM D3227) content of 5.36wt. %, 1.8 SH/molecule, or 1.67 meq SH/g. Combustion analysis indicatedC, 65.67%, H, 10.17%, N, 0.34%, and S, 9.84%.

Example 8 CPC407-97

Epoxidized soybean oil (600 g, ˜0.6 mol) and1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 5.0 g, 32.4 mmol) were chargedto a 1-L Hastelloy C autoclave reactor that was pressure tested to 630psig. Hydrogen sulfide (H₂S, 204.0 g, 5.99 mol) was then pressured intothe stirred reactor contents through a dip tube in the liquid space. Thereaction mixture was heated and maintained at 85° C. with stirring for 4hrs, during which time the reactor pressure decreased from a maximum of577 psig to 519 psig. The stirrer was stopped and while still warm(80-85° C.), excess H₂S was slowly vented to a low-pressure flare. Thereactor vapor space was then swept with N₂ for 1 hr and the reactorcontents drained warm (80-85° C.). The reaction product was N₂ spargedunder vacuum (<50 mmHg) at 130-140° C. for 16 hrs to remove residualH₂S. The resulting light yellow, viscous sticky oil had a thiol sulfur(titration with AgNO₃) content of 5.85 wt. %, 2.0 SH/molecule, or 1.82meq SH/g. Combustion analysis indicated C, 65.09%, H, 10.15%, N, 0.35%,and S, 10.63%.

Example 9 CPC407-98

Epoxidized soybean oil (600 g, ˜0.6 mol) and1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, 5.0 g, 32.4 mmol) were chargedto a 1-L Hastelloy C autoclave reactor, and the vessel was pressuretested to 630 psig. Hydrogen sulfide (H₂S, 204.0 g, 5.99 mol) was thenpressured into the stirred reactor contents through a dip tube in theliquid space. The reaction mixture was heated and maintained at 85° C.with stirring for 2 hrs, during which time the reactor pressuredecreased from a maximum of 577 psig to 508 psig. The stirrer wasstopped and while still warm (80-85° C.), excess H₂S was slowly ventedto a low-pressure flare. The reactor vapor space was then swept with N₂for 1 hr and the reactor contents drained warm (80-85° C.). The reactionproduct was N₂ sparged under vacuum (<5 mmHg) at 130-140° C. for 16 hrsto remove residual H₂S. The resulting light yellow, viscous sticky oilhad a thiol sulfur (titration by modified ASTM D3227) content of 5.07wt. %, 1.7 SH/molecule, or 1.58 meq SH/g. Combustion analysis indicatedC, 63.96%, H, 10.01%, N, 0.35%, and S, 11.22%.

Table 5 provides the properties of the mercaptohydroxy soybean oilsamples produced in Examples 1-10.

TABLE 5 Mercaptan Epoxides Reaction Reaction Sulfur SH per groups leftper Epoxide:SH Example Time (hrs) Temp (° C.) (wt. %)¹ molecule²molecule³ Molar Ratio 1 0 N/A N/A 0 4.3 — 2 8 85 7.53 2.5 1.8 0.72 3 1497 4.14 1.4 2.9 2.07 4 10 85 8.28 2.8 1.5 0.54 5 12 85 8.24 2.8 1.5 0.546 8 85 7.34 2.5 1.8 0.72 7 6 85 5.93 2.0 2.3 1.15 8 4 85 5.36 1.8 2.51.40 9 4 85 5.85 2.0 2.3 1.15 10 2 85 5.07 1.7 2.6 1.529 ¹Thiol sulfurwas determined by silver nitrate oxidation using ASTM D 3227 ²Determinedby wt. % thiol sulfur ³Determined by subtracting the SH/molecule fromthe starting material epoxide content

Example 1L

Additional mercaptohydroxy soybean oils were prepared using differentquantities of epoxidized soybean oil, hydrogen sulfide, and catalystusing different temperature and reaction times. The general procedureused to produce the mercaptohydroxy soybean oils is provided as follows.

Epoxidized soybean oil and the catalyst were charged to a 1-L HastelloyC autoclave reactor, and the vessel was pressure tested to 1000 psig.Hydrogen sulfide was then pressured into the stirred reactor contentsthrough a dip tube in the liquid space. The reaction mixture was heatedand maintained at temperature a set period of time with stirring for 12hrs. During the reaction time the reactor pressure usually decreased. Atthe end of the reaction time, the stirrer was stopped and excess H₂S wasslowly vented while the reaction mixture was warm to a low-pressureflare. The reactor vapor space was then swept with N₂ for 1 hr and thereactor contents drained. The reaction product was N₂ sparged undervacuum (<50 mmHg) at 100° C. for 16 hrs to remove residual H₂S. Table 6provides the reaction conditions used to produce the mercaptohydroxysoybean oils for several runs and the thiol sulfur content of themercaptohydroxy soybean oils produced.

TABLE 6 Mecaptohydroxy Soybean Oil Production Runs Epoxidized SoybeanOil Catalyst H₂S H₂S:Epoxide Temperature Time Thiol Sulfur^(a) Run (g)(g) (g) Molar Ratio (° C.) (minutes) (wt. %) 556-41† 249.6 1.950 214.05.86 64 728 5.69 556-53^(†) 250.0 2.000 213.0 5.81 100 370 9.04556-47^(†) 250.5 1.050 213.0 5.81 101 720 10.47 407-81D^(†) 500.0 4.200255.0 3.49 85 480 7.53 407-86^(†) 600.0 5.000 204.0 2.07 85 600 8.28556-79^(‡) 250.0 2.600 214.0 5.83 100 720 6.68 556-80^(‡) 251.0 5.000214.0 5.81 100 720 9.51 ^(†)Catalyst was DBU ^(‡)catalyst wastriethylamine (TEA) ^(a)Thiol sulfur measured by silver nitratetitration using modified ASTM D 3227

Run number 407-86 was subjected to the sodium methoxide methanolysisprocedure and subsequently analyzed by GC/MS. The GS/MS analysisindicated that the product had epoxide group to thiol group molar ratioof approximately 0.14. The methanolysis data also indicated that anaverage of 80.4 percent of the product mercaptohydroxy soybean oilcontained sulfur.

Oligomerized MSO (Mercaptanized Soybean Oil)

Example 1

Mercaptanized soybean oil (900.1 g; 10.92 wt. % thiol sulfur) wascharged to a three necked flask along with elemental sulfur pellets (9.6g). The reaction mixture was heated to 120° C. until sulfur dissolvedand then cooled to 99° C. Tributylamine (4.8 g) was charged to thereaction mixture with an addition funnel drop wise. The reaction mixturewas mixed at 90° C. for 2 hrs. H₂S evolution was observed. The reactionproduct (904.8 g) was sparged with N₂ under vacuum at 110° C. for 4 hrsto remove residual H₂S. The final product was a light yellow oil with athiol sulfur of 6.33 wt. % (by modified ASTM D3227). The elementalcombustion analysis was 70.19% C, 10.37% H; and 11.21% S.

Example 2

Mercaptanized soybean oil (900.0 g; 10.92 wt. % thiol sulfur) wascharged to a three necked flask along with elemental sulfur pellets(36.0 g). The reaction mixture was heated to 120° C. until sulfurdissolved and then cooled to 100° C. Tributylamine (4.8 g) was chargedto the reaction mixture with an addition funnel drop wise. The reactionmixture was mixed at 90° C. for 36 hrs. H₂S evolution was observed. Thereaction product (825.6 g) was sparged with N₂ under vacuum at 90° C.for 36 hrs to remove residual H₂S. The reaction product was then spargedwith N₂ under vacuum at 110° C. for 3 hrs to remove residual H₂S. Thefinal product was a light yellow oil with a thiol sulfur of 2.36 wt. %(by modified ASTM D3227). The elemental combustion analysis was 68.90%C, 11.07% H; and 12.25% S.

Example 3

Mercaptanized soybean oil (900.1 g; 10.92 wt. % thiol sulfur) wascharged to a three necked flask along with elemental sulfur pellets(18.0 g). The reaction mixture was heated to 125° C. until sulfurdissolved and then cooled to 101° C. Tributylamine (4.8 g) was chargedto the reaction mixture with an addition funnel drop wise. The reactionmixture was mixed at 90° C. for 2 hrs. H₂S evolution was observed. Thereaction product (901.5 g) was sparged with N₂ under vacuum at 110° C.for 4 hrs to remove residual H₂S. The final product was a light yellowoil with a thiol sulfur of 4.9 wt. % (by modified ASTM D3227). Theelemental combustion analysis was 69.58% C, 11.25% H; and 11.31% S.

Example 4

Mercaptanized soybean oil (900.2 g; 10.92 wt. % thiol sulfur) wascharged to a three necked flask along with elemental sulfur pellets(45.0 g). The reaction mixture was heated to 125° C. until sulfurdissolved and then cooled to 100° C. Tributylamine (4.8 g) was chargedto the reaction mixture with an addition funnel drop wise. The reactionmixture was mixed at 90° C. for 2 hrs. H₂S evolution was observed. Thereaction product (915.0 g) was sparged with N₂ under vacuum at 110° C.for 4 hrs to remove residual H₂S. The final product was a light yellowoil with a thiol sulfur of 1.41 wt. % (by modified ASTM D3227). Theelemental combustion analysis was 68.35% C, 10.98% H; and 13.28% S.

Table 7 provides the viscosities of the oligomerized mercaptanizedsoybean oil (cross-linked mercaptanized soybean oil) produced inexamples 1-4 at several different temperature.

TABLE 7 Viscosities of Oligomerized MSO 25° C. Viscosity 50° C. 75° C.100° C. Example (cP) Viscosity (cP) Viscosity (cP) Viscosity (cP) 1610.5 162.8 52.14 29.60 2 3240 — 200 106.3 3 843 321.7 68.8 38.54 >10000 1502 398 213 Determined by Brookfield Viscometer

The different oligomeric mixtures were analyzed by GPC. The GPC datashowed the presence of various oligomers including up to 20 triglycerideunits linked together.

Polythiourethane Polymer Preparation

Mercaptanized Soybean Oil (MSO), Mercaptohydroxy Soybean Oil (MHSO), orCross-linked Mercaptanized Soybean Oil (CMSO—Oligomerized MSO) (allreferred to hereafter as cross-linking agent) was weighed into apolyethylene beaker. To the cross-linking agent was added the desiredpolyisocyanate. To this reaction mixture was added the desired catalyst.The three-component reaction mixture was then manually stirred with awooden Popsicle stick. The entire pre-polymer mixture was then pouredinto the appropriate mold for curing. Example molds include 50 mmdiameter or 70 mm diameter aluminum pans. The sample was then cured viathe desired profile, A, B, or C. After the cure time was complete, thesample was stored at room temperature in plastic, resealing, sandwichbags for 2 weeks. The sample was then removed from the aluminum mold andeither tested by ASTM D2240-O₂B, ASTM E1545-95A and/or E228-95 orresealed in the sandwich bag for storage.

Polythiourethane Compositions

TABLE 8 R&T Feedstocks Diisocyanates Stoichiometry CatalystsMSO-trifunctional LuprinateTM - ≈0.9 DABCO PolyMDI MSO-difunctional MDI≈1 DBTDL MSO-TBP treated HMDI ≈1.25 Jeffol ® A-480 MHSO - trimercaptanTDI MHSO - dimercaptan HDI CMSO - hi cross-link CMSO - med cross-linkCMSO - low cross-link Castor Oil

Numerous polythiourethane compositions were prepared by reacting a thiolester composition with a diisocyanate in the presence of a catalyst byusing the processes described herein for preparing such polythiourethanecompositions. The compositions were produced using the differentvariables of feedstocks, diisocyanates, stoichiometry, and catalystsshown in Table 8. Once every combination of variable was used, over 1200compositions were produced. Each of the feedstocks were reacted witheach of the diisocyanates at each of the stoichiometries with each ofthe catalysts listed to produce the 1200+compositions. The stoichiometrywas based upon a thiol ester composition (MSO, MHSO, CMSO, MCO) activehydrogen (thiol and hydroxyl group) to diisocyanate equivalent ratio.For example, caster oil was reacted with toluene diisocyanate at astoichiometric value of 1.25 while using Jeffol® A480 as the catalyst.As another example, a thiol ester composition was reacted with methanediisocyanate at a stoichiometric value of 0.9 while using the DABCOcatalyst.

In addition polythiourethanes produced from the matrix above twopolythiourethanes were produced from mercaptanized castor oil (MCO).

In the first MCO polythiourethane example, MCO was weighed into apolyethylene beaker. To the MCO agent was added Luprinate at a thiol toisocyanate mole ratio of 0.95. To this reaction mixture was addeddibutyl tin dilaurate (DBTDL) at a weight percent of 0.125 based uponthe total weight of the ingredients. The three-component reactionmixture was then manually stirred with a wooden Popsicle stick. Theentire pre-polymer mixture was then poured into a mold for curing andcured using curing profile B. After the curing time was complete it wasdetermined that the preparation produced a polythiourethane polymer.

In the second MCO polythiourethane example, MCO was weighed into apolyethylene beaker. To the MCO agent was added Luprinate M20S at athiol to isocyanate mole ratio of 1.00. To this reaction mixture wasadded dibutyl tin dilaurate (DBTDL) at a weight percent of 0.125 basedupon the total weight of the ingredients. The three-component reactionmixture was then manually stirred with a wooden Popsicle stick. Theentire pre-polymer mixture was then poured into a mold for curing andcured using curing profile B. After the curing time was complete it wasdetermined that the preparation produced a polythiourethane polymer.

In the polythiourethane compositions, the feedstock thiol estercompositions that were used included MSO (mercaptanized soybean oil),MHSO (mercaptohydroxy soybean oil), CMSO (cross-linked mercaptanizedsoybean oil), castor oil, and MCO (mercaptanized caster oil). Thediisocyanates that were used to produce these compositions included MDI(4,4′-methylenebis(phenyl) diisocyanate), HMDI(4,4′-methylenebis(cyclohexyl) diisocyanate, which is also known ashydrogenated MDI), TDI (tolylene 2,4-diisocyanate), HDI(1,6-diisocyanatohexane, which is also known as hexamethylenediisocyanate), and Luprinate™ M20S (which is an oligomerized form of MDIand is also referred to as polymeric MDI that is produced by BASFCorporation). The catalysts that were used included DABCO(diazabicyclooctane—di-tertiary amine), DBTDL (dibutyl tindilaurate—organometallic catalyst), Jeffol® A-480 (which is a tertiaryamine polyol produced by Huntsman Based Chemicals), and BDMA(benzyldimethylamine).

Various physical properties were determined for randomly selectedpolythiourethane compositions of the 1200+compositions, the results ofwhich are included in tables that are attached as FIGS. 7A-7F. Thecuring profiles that were used are as follows: A=curing for ˜1-8 hoursat room temperature, followed by curing at 65° C. overnight, and thencuring at 95° C. for 8 hours; B=curing at 65° C. overnight, followed bycuring at 95° C. for 24 hours; and C=curing at 120° C. for 3 hours,followed by curing at 95° C. for 24 hours. CTE 1 represents thecoefficient of thermal expansion between the glass transitiontemperature and a first transition temperature. CTE 2 represents thecoefficient of thermal expansion between the first transitiontemperature and a second transition temperature.

FERTILIZER EXAMPLES

Embodiments of the present invention will be illustrated with referenceto the following examples that should not be used to limit or construethe invention. Those of ordinary skill in the art will readilyappreciate that the specific conditions and methodology noted in theFertilizer Examples can be varied to produce the same or similarcompositions. Unless otherwise noted, all temperatures are degreesCelsius and all ingredient amounts percentages are by weight.

In the Fertilizer Examples, the following materials were used:

A: Fertilizer particles—granular fertilizer grade urea, SGN 250,commercially available from Agrium;

B1: Mercaptanized soybean oil (an example of MVO discussedabove)—Polymercaptan 358, available from Chevron Phillips Chemical Co.;8.65% thiol sulfur; 370 equivalent weight; viscosity of 510.6 cSt@21°C.;

B2: Mercapto-hydroxy soybean oil (an examples of MHVO discussed above)—Amercapto-hydroxy soybean oil made by the free radical addition ofhydrogen sulfide to epoxidized soybean oil; the mercapto and hydroxyfunctionalities are equal; 8.335% thiol sulfur; equivalent weight 192(including both mercapto and hydroxy functionalities);

B3: Sulfur cross-linked mercaptanized soybean oil (an example of CMVOdiscussed above)—A sulfur cross-linked mercaptanized soybean oil made bythe addition of elemental sulfur to mercaptanized soybean oil; thiolsulfur content 6.33%; equivalent weight 506;

B4: Sulfur cross-linked mercaptanized soybean oil (an example of CMVOdiscussed above)—A sulfur cross-linked mercaptanized soybean oil made bythe addition of elemental sulfur to mercaptanized soybean oil; thiolsulfur content 7.64%; equivalent weight 419; cross-linkcross-link

C1: Isocyanate #17—A polymeric MDI, commercially available from BASFCanada, equivalent weight of 133;

C2: Epoxy resin—5 minute epoxy resin, commercially available from ITWDevcon, Danvers, MA 01923 USA, equivalent weight 198;

D1: Organic additive—Gulftene C30-HA alpha olefin wax, commerciallyavailable from Chevron Phillips Chemical Co., melting point 65° C.-80°C.;

D2: Organic additive—Calwax 170, a microcrystalline wax commerciallyavailable from Calwax Corporation;

E: Cross-linking agent—Jeffol A480, commercially available from HuntsmanPolyurethanes; equivalent weight of 120; functionality 4.0; viscosity of4000 cPs @25C;

F1: Amine catalyst: Exp-9, commercially available from HuntsmanPolyurethanes; and

F2: Amine catalyst: 1,8-Diazabicyclo[5,4,0]undec-7-ene (DBU), CAS#6674-22-2.

Fertilizer Examples 1-6

A series of CRF materials were produced using the formulations set outin Table 4 using the following methodology. The amount of fertilizersparticles (A) coated in each Fertilizer Example was 1000 g.

A stainless steel coating drum, 12 inches in diameter by 6 inches deep,with an enclosed back plate and a front plate that had an 8 inch centralopening was used. The coating drum was fitted with four evenly spacedlongitudinal baffles, each about V₂ inch high. The coating drum wasconnected to a variable speed drive, set to rotate the drum at 18 rpm.

During the process, the internal temperature of the drum and itscontents was maintained at about 70° C. by using a variable speedelectric heating gun. The coating components were added using individualautomatic macro pipettes capable of adding ⅓ the weight of each coatingcomponent in a single addition. In other words, the coating was appliedin 3 layers—the total coating weight is reported in Table 4. InFertilizer Examples, 2, 3 and 6, a wax overcoat was applied afterapplication of the 3-layered coating. At the end of the process, thedrum and its contents were cooled to 40° C. by blowing a stream of roomtemperature air into the drum. The contents were removed and stored in aplastic bag.

A Paint shaker test was used to evaluate the mechanical handlingdurability of each product of the Fertilizer Examples. The “Paint shakersimulation” test used to simulate the damage to the controlled releasecoating is conducted in a paint shaker machine using the followingmethodology.

First 200 grams of the slow release fertilizer is placed in a 6″diameter by 5.5″ deep metal can with lid. Then 8 (¼ inch by ½ inch)machine bolts with slotted heads and 8 (¼ inch) square head nuts areadded in the can. The can with the slow release fertilizer, nuts, andbolts is then placed securely in a paint conditioner/shaker (Red Devil,¼ H.P. model). The test sample is vigorously conditioned in the paintshaker at frequency of 730 cycles per minute for 6 minutes. Theoperating time is controlled with an electronic timer (Gralab model 451)that automatically stops the paint shaker at the preset time. After thepaint shaker cycling is complete the can is removed and the nuts andbolts are removed by passing the contents through a 3½ mesh screen. Theslow release fertilizer is collected in a pan and returned to its samplebag for the release rate analysis.

A comparison test has been conducted to correlate the simulation effectof the paint shaker with the damage in some commercial fertilizerblenders. The operating time of the paint shaker and the number of thebolts and nuts are determined based on the comparison test. Thepresetting of these parameters in the test for the work in this patentcan simulate properly the damage in the commercial fertilizer blenders.

The water release rate profile for the slow release fertilizer materialbefore and after the Paint shaker simulation test was then determined.In the analysis, a Technicon AutoAnalyzer™ was calibrated and usedpursuant to the teachings of Automated Determination of Urea andAmmoniacal Nitrogen (University of Missouri, 1980). The followingprocedure was used:

-   -   1. Accurately weigh 15 grams (±0.1 mg) of the sample into a        weigh dish. Record the weight of sample. Transfer the sample to        125 mL Erlenmeyer flask.    -   2. Add 75 mL of demineralized water and stopper the flask.    -   3. Gently swirl the sample and water until all the particles are        submersed.    -   4. Let the sample stand for a specified time at a constant        temperature (typically at room temperature).    -   5. Gently swirl the flask to mix the solution and decant only        the solution to a 100 mL volumetric flask.    -   6. Rinse the sample with demineralized water adding to the        volumetric flask.    -   7. Bulk to volume of volumetric flask and mix thoroughly.    -   8. If the test is to be repeated for another time period, repeat        starting at Step 2.    -   9. Once the Technicon AutoAnalyzer II is on line, transfer some        of this solution (or perform the required dilutions if        necessary) to the Technicon sample cups for analysis.    -   10. Record the results as parts per million N—NH₃ (read directly        from a Shimadzu Integrator)

The water release performance for the CRF material produced inFertilizer Examples 1-3 is shown in FIG. 8—in each case, the waterrelease performance is shown both before and after Paintshaker handlingtest. The water release performance for the CRF material produced inFertilizer Examples 4-6 is shown in FIG. 9—in each case, the waterrelease performance is shown both before and after Paintshaker handlingtest.

The results in FIGS. 7 and 8 illustrate that a polythiourethane coatingcan be made using mercaptanized soybean oil to produce a CRF materialhaving desirable slow release properties. These results also illustratethat the release performance can be controlled by selection of theorganic additive (e.g., wax).

Fertilizer Examples 7-10

A series of CRF materials were produced and tested using the methodologyreported above for Fertilizer Examples 1-6 and the formulations set outin Table 5A.

The water release performance for the CRF material produced inFertilizer Examples 7-10 is shown in FIG. 9—in each case, the waterrelease performance is shown both before and after Paintshaker handlingtest.

The results in FIG. 9 illustrate that a polythiourethane coating can bemade using sulfur cross-linked mercaptanized soybean oil to produce aCRF material having desirable slow release properties. These resultsalso illustrate that the addition of a cross-linking agent to thecoating formulation can be used to reduce the release rate of the coatedfertilizer.

Fertilizer Examples 11-14

A series of CRF materials were produced and tested using the methodologyreported above for Fertilizer Examples 1-6 and the formulations set outin Table 6A.

The water release performance for the CRF materials produced inFertilizer Examples 11-14 is shown in FIG. 10—in each case, the waterrelease performance is shown both before and after Paintshaker handlingtest.

The results in FIG. 10 illustrate that a polythiourethane coating can bemade using mercapto-hydroxy soybean oil to produce a CRF material havingdesirable slow release properties. These results also illustrate that apolythiourethane coating can be made using a mixture of a mercaptanizedsoybean oil and a mercapto-hydroxy soybean oil to produce a CRF materialhaving desirable slow release properties.

Fertilizer Examples 15-17

A series of CRF materials were produced and tested using the methodologyreported above for Fertilizer Examples 1-6 and the formulations set outin Table 7A.

The water release performance for the CRF materials produced inFertilizer Examples 15-17 is shown in FIG. 11—in each case, the waterrelease performance is shown both before and after Paintshaker handlingtest.

The results in FIG. 11 illustrate that an epoxy polymer coating can bemade using mercapto-hydroxy soybean oil to produce a CRF material havingdesirable slow release properties.

While this invention has been described with reference to illustrativeembodiments and examples, the description is not intended to beconstrued in a limiting sense. Thus, various modifications of theillustrative embodiments, as well as other embodiments of the invention,will be apparent to persons skilled in the art upon reference to thisdescription. It is therefore contemplated that the appended claims willcover any such modifications or embodiments.

All publications, patents and patent applications referred to herein areincorporated by reference in their entirety to the same extent as ifeach individual publication, patent or patent application wasspecifically and individually indicated to be incorporated by referencein its entirety.

Analysis

Analysis of the Thiol Containing Esters, Hydroxy Thiol Containing Estersand Cross-Linked Thiol Containing Ester

Particular aspects of the thiol containing esters, hydroxy thiolcontaining esters, cross-linked thiol ester, unsaturated esters andepoxidized unsaturated esters are measured particular analyticaltechniques. Thiol sulfur values were obtained using a silver nitratetitration as described in ASTM D3227 or by Raman spectroscopy.Carbon-carbon double bond to thiol group molar ratio, cyclic sulfide tothiol group molar ratios were determined by ¹³C NMR and/or GC analysisof the thiol containing ester or hydroxy thiol containing ester sidechains.

Thiol Sulfur Content by Raman Spectroscopy

Thiol sulfur content was measured by both silver nitrate titration, ASTMD3227, and/or Raman spectroscopy. The Raman spectroscopy method ispracticed by measuring the Raman spectra of the thiol containing ester,hydroxy thiol containing ester, cross-linked thiol ester and comparingthe spectra to calibration standards containing know thiol compoundshaving know amounts of thiol groups. Generally, the calibration standardthiol compound has a similar structure to the thiol containing estersanalyzed.

The thiol containing esters, hydroxy thiol containing esters andcross-linked thiol ester thiol content were determined by comparing theRaman spectra of the thiol containing esters, hydroxy thiol containingesters and cross-linked thiol ester to calibration standards preparedfrom mercaptanized methyl oleate diluted in soybean oil to known thiolsulfur contents. Thiol sulfur calibration standards were prepared usingstandards using various known concentration of mercaptanized methyloleate diluted in soybean oil.

Raman spectra of the calibration standards and the thiol containingesters, hydroxy thiol containing esters and cross-linked thiol esterwere measured using a Kaiser Hololab 5000 Process Raman spectrometer,using a 785 nm laser. Thiol containing esters, hydroxy thiol containingesters and cross-linked thiol ester samples and the thiol sulfurcalibration standard Raman spectra were obtained by collecting four 10second scans which were then processed using Holoreact software. Thiolsulfur values for the thiol containing esters, hydroxy thiol containingesters and cross-linked thiol ester were then calculated using the ratioof the peak area values of the thiol SH peak (center: 2575 cm-1; area2500-2650 cm-1), and the C═O peak (center—1745 cm-1; area—1700-1800cm-1) and comparing them to the peak area values for the calibrationstandards and interpolating the containing esters, hydroxy thiolcontaining esters and cross-linked thiol ester thiol sulfur contents.Repeatability of the thiol sulfur values as measured by Ramanspectroscopy have been shown to have a standard deviation of 0.05-0.1and a % RSD of 0.6-1.5 using 5 samples having a % thiol sulfur contentranging from 3.1-10.6 weight percent as measured over a two monthperiod.

The Raman spectroscopy technique for determining the thiol sulfurcontent of a thiol containing ester, hydroxy thiol containing ester, anda cross-linked thiol containing ester has been illustrated using a thiolcontaining ester produced from soybean oil. However, one skilled in theart may adapt and apply the Raman spectroscopy technique for determiningthe thiol sulfur content of other thiol containing esters, hydroxy thiolcontaining esters, and a cross-linked thiol containing esters describedherein.

C═C to Thiol Group and Cyclic Sulfide Group to Thiol Group Molar Ratiosby ¹³C NMR

Carbon-carbon double bond to thiol group molar ratio and cyclic sulfidegroup to thiol group molar ratios were determined by ¹³C NMR. Thiolcontaining ester ¹³C NMR spectra were obtained on a Varian MercuryINOVA400 NMR, a Varian Mercury Plus 300 NMR, or equivalent spectrometer(75.5 MHz ¹³C NMR). Peak areas were determined for the cyclic sulfidecarbon atoms, thiol group HS—C carbon atoms and carbon-carbon doublebonds carbon atoms using the ¹³C NMR regions indicated in the tablebelow:

Number of Carbon Functional Group ¹³C NMR Region Atoms/Group CyclicSulfide Carbon Atoms 49-49.5 ppm 2 HS—C Carbon Atoms 40-41.5 ppm 1 C═CCarbon Atoms  120-140 ppm  2

The thiol containing ester cyclic sulfide to thiol group molar ratiowere calculated by dividing the cyclic sulfide carbon atoms ¹³C NMR peakarea by 2 (to account for the 2 carbon atoms per cyclic sulfide group)and dividing the resultant number by the thiol group HS—C carbon atoms¹³C NMR peak area. The thiol containing ester carbon-carbon double bondto thiol group molar ratio were calculated by dividing the C═C carbonatoms ¹³C NMR peak area by 2 (to account for the 2 carbon atoms percarbon-carbon double bond) and dividing the result number by the thiolgroup HS—C carbon atoms ¹³C NMR peak area. Offset sample ¹³C NMR's forsoybean oil and a thiol containing ester produced from soybean oil usingthe disclosed process is provided as FIG. 1.

The number of average number carbon-carbon double bonds per unsaturatedester molecule can be determined utilizing similar methods utilizingeither the carbonyl group carbon atom or the C—O ester group carbon atom¹³C NMR peak areas in conjunction with the carbon-carbon double bond ¹³CNMR peak area.

The NMR technique for analyzing the unsaturated ester and the thiolcontaining ester produced from an unsaturated ester have beenillustrated using ¹³C NMR on soybean oil the thiol containing esterproduced from soybean oil. However, one skilled in the art may adapt andapply either the ¹³C NMR or ¹H NMR technique to analyze the unsaturatedesters and thiol containing ester produced from the unsaturated esterdescribed herein.

Epoxide Group to Thiol Group Molar Ratios by ¹³C or ¹H NMR

The epoxide group to thiol group molar ratios were determined using ¹Hor ¹³C NMR. Hydroxy thiol containing ester ¹H or ¹³C NMR spectra wereobtained on a Varian Mercury INOVA400 NMR, a Varian Mercury Plus 300NMR, or equivalent spectrometer (300 MHz ¹H NMR—75.5 MHz ¹³C NMR). Peakareas were determined for the epoxide group and sulfide group using the¹³C and or ¹H regions indicated in the table below:

Number of Number of Carbon Hydrogen Functional ¹H NMR ¹³C NMR Atoms/Atoms/ Group Region Region Group Group Epoxide Group 2.75-3.2 ppm53.6-56.6 ppm 2 2 Carbon Atoms HS—C Carbon   3.2-4 ppm   40-41.5 ppm 1 1Atoms

The hydroxy thiol containing ester epoxide group to thiol group molarratio were calculated by dividing the epoxide group carbon atoms ¹H NMRpeak area by 2 (to account for the 2 hydrogen atoms attached to theepoxide group carbon atoms) and dividing the result number by the thiolgroup HS—C carbon atom hydrogens IC NMR peak area. Similarly, thehydroxy thiol containing ester epoxide group to thiol group molar ratiowere calculated using ¹³H NMR peak areas.

The average number of epoxide group per epoxidized unsaturated estermolecule can be determined utilizing similar methods utilizing eitherthe carbonyl group carbon atom or the C—O ester group carbon atoms ¹³CNMR peak areas in conjunction with the epoxide group ¹³C NMR peak area.Sample ‘H NMR’s epoxidized soybean oil and a thiol containing esterproduced from epoxidized soybean oil lare provided in FIG. 2.

The NMR technique for analyzing the epoxidized unsaturated ester and thethiol containing ester produced from an epoxidized unsaturated ester (ahydroxy thiol containing ester) has been illustrated using ¹H NMR onepoxidized soybean oil the thiol containing ester produced fromepoxidized soybean oil. However, one skilled in the art may adapt andapply either the ¹H NMR or ¹³C NMR technique to analyze the epoxidizedunsaturated esters and thiol containing ester produced from theepoxidized unsaturated ester described herein.

Analysis of Unsaturated Esters, Epoxidized Unsaturated Esters, ThiolContaining Esters, and Hydroxy Thiol Containing Esters by Methanolysis

Many properties of the unsaturated esters, epoxidized unsaturatedesters, thiol containing esters, and hydroxy thiol containing ester wereand/or can be determined by converting the complex ester molecules intotheir component polyols and carboxylic acid methyl esters. The convertedesters are then analyzed by gas chromatography (GC) and/or gaschromatography/mass spectrometry (GCMS) to determine the composition ofthe complex ester side chains. Properties that are or can be determinedby the methanolysis followed by GC or GC/MS of the carboxylic acidmethyl esters include the number of side chain that contain thiolgroups, the percent of thiol group sulfur, the number of (or averagenumber) of double bonds per ester molecule, the molecular weightdistribution (or average molecular weight) of the ester side chains, thenumber of (or average number of) epoxide groups per ester molecule, thecyclic sulfide to thiol group molar ratio, the carbon-carbon double bondto thiol group molar ratio, and the epoxide group to thiol group molarratio, among others.

Depending upon the material being subjected to the methanolysisprocedure, there are two methanolysis procedures that were practicedupon the unsaturated ester, epoxidized esters, thiol containing ester,and hydroxy thiol containing esters described within the experimentalsection.

Unsaturated esters and thiol containing ester produced from unsaturatedester were subjected to a hydrogen chloride based methanolysisprocedure. In the hydrogen chloride methanolysis procedure, a 50 to 100mg sample of the thiol containing ester is contacted with 3 mL of 3 Nmethanolic HCl and reacted for 2 hours a 50° C. The solution is thenallowed to cool and the neutralized with a dilute sodium bicarbonatesolution. The solution's organic components are then extracted withethyl ether and analyzed by GC and/or GC/MS. Additional details for themethanolic hydrogen chloride methanolysis procedure may be found in theproduct specification sheet for methanolic HCl, 0.5 N and 3 N assupplied by Supelco.

Epoxidized unsaturated esters and hydroxy thiol containing estersproduced from epoxidized unsaturated esters were subjected to a sodiummethoxide based methanolysis procedure. The sodium methoxidemethanolysis procedure was based upon the procedure disclosed in U.S.Pat. No. 3,991,089. In the sodium methoxide methanolysis procedure,approximately 1 g of the ester was placed in a 50 mL vial with 5.0 mL25% sodium methoxide in methanol, and 10 mL methanol. The mixture wasshaken for approximately 1 hour at room temperature, during which timethe solution became one phase. The mixture was then poured into 25 mL ofdistilled water. Diethyl ether, 25 mL, was added to the solution and themixture was acidified with 0.5 N HCL to a pH of approximately 5. Theorganic layer was separated from the aqueous layer using a separatoryfunnel. The organic layer was washed successively with distilled water(15 mL) and brine solution (15 mL) and then dried over magnesiumsulfate. The magnesium sulfate was separated from the organic solutionby filtration and the solvent removed by rotary evaporation.

The products of the methanolysized esters of either methanolysisprocedure were then subjected to GC and or GC/MS analysis. Two potentialGC and/or GC/MS columns and analysis conditions are provided below:

TABLE 8 Methanolysis Products - GC or GC/MS Analysis Conditions 1Analysis Column HP-5 30 m × 0.32 mm id × 0.25 μm film thickness GCColumn GC Analysis Conditions: Initial Oven Temperature 60° C. InitialTime 5 minutes Oven Temperature Ramp Rate 8° C./minute Final OvenTemperature 260° C. Final Time 20 minutes Injector Temperature 250° C.Detector Temperature 300° C. Column Helium flow 1 mL/minute

TABLE 9 Methanolysis Products - GC or GC/MS Analysis Conditions 2Analysis Column DB 30 m × 0.25 mm id × 0.25 μm film thickness GCAnalysis Conditions: Initial Oven Temperature 100° C. Initial Time 10minutes Oven Temperature Ramp Rate 5° C./minute Final Oven Temperature270° C. Final Time 10 minutes Injector Temperature 250° C. DetectorTemperature 300° C. Column Helium flow 2 mL/minute

Table 10 provides the GC/MS trace peak assignments for a GC/MS trace ofa soybean oil subjected to the methanolysis procedure and analyzed byGC/MS using a HP-5 30 m×0.32 mm id×0.25 μm film thickness GC Column.

TABLE 10 GC/MS Data for Methanolysis of Soybean Oil GC Methyl EsterCarboxylic Retention time Acid Assignment 21.58 Methyl hexadecanoate23.66 Methyl (C18 monoene)oate 23.74 Methyl (C18 monoene)oate 23.96Methyl octadecanoate

FIG. 3 provides a GC/MS trace of a mercaptanized soybean oil subjectedto the methanolysis procedure and analyzed by GC/MS using a HP-5 30m×0.32 mm id×0.25 μm film thickness GC Column. Table 11 provides theGC/MS trace peak assignments.

TABLE 11 GC/MS Data for Methanolysis of A Thiol Containing EsterProduced from Soybean Oil GC Retention time Methyl Ester Carboxylic AcidAssignment 21.58 Methyl hexadecanoate 23.66 Methyl (C18 monoene)oate23.74 Methyl (C18 monoene)oate 23.96 Methyl octadecanoate 26.46 Methyl(C18 Monoene monomercaptan)oate 26.59 Methyl (C18 Monoenemonomercaptan)oate 26.66 Methyl (C18 Monoene monomercaptan)oate 26.80Methyl (C18 monomercaptan)oate 27.31 Methyl (C18 cyclic sulfide)oate27.44 Methyl (C18 cyclic sulfide)oate 29.04 Methyl (C18 dimercaptan)oate29.15 Methyl (C18 dimercaptan)oate 29.37 Methyl (C18 monoenedimercaptan)oate 29.46 Methyl (C18 monoene dimercaptan)oate 30.50 Methyl(C18 di (cyclic sulfide))oate Peaks at 29.37 or 29.46 could also containMethyl (C18 cyclic sulfide monomercaptan)oate isomers as part of thosepeaks.

FIG. 4 provides a GC/MS trace of epoxidized soybean oil subjected to themethanolysis procedure and analyzed by GC/MS using a HP-5 30 m×0.32 mmid×0.25 μm film thickness GC Column. Table 12 provides the GC/MS tracepeak assignments.

TABLE 12 GC/MS Data for Methanolysis of Epoxidized Soybean Oil GCRetention time Methyl Ester Carboxylic Acid Assignment 16.09 Methylhexadecanoate 17.68 Methyl octadecanoate 18.94 Methyl (C18monoepoxide)oate 19.94 Methyl (C18 diepoxide)oate 20.14 Methyl (C18diepoxide)oate 21-21.5 Methyl (C18 triepoxide)oate

FIG. 5 provides a GC/MS trace of an epoxidized soybean oil contactedwith hydrogen sulfide (a hydroxy thiol containing ester) subjected tothe methanolysis procedure and analyzed by GC/MS using a HP-5 30 m×0.32mm id×0.25 μm film thickness GC Column. Table 13 provides the GC/MStrace peak assignments.

TABLE 13 GC/MS Data for Methanolysis of a Hydroxy Thiol Containing EsterProduced from Epoxidized Soybean Oil GC Retention time Methyl EsterCarboxylic Acid Assignment 16.09 Methyl hexadecanoate 17.68 Methyloctadecanoate 18.94 Methyl (C18 monoepoxide)oate 19.94 Methyl (C18diepoxide)oate 20.14 Methyl (C18 diepoxide)oate 20.75 Methyl (C18monohydroxy monothiol)oate 21-21.5 Methyl (C18 triepoxide)oate 22.82Methyl (C18 dihydroxy dithiol)oate 22.90 Methyl (C18 monoepoxidemonohydroxy monothiol)oate 27-27.5 Unidentified mixture of C18 sulfurcontaining methyl esters

The methanolysis procedure and GC/MS procedure has been illustrate usingsoybean oil, epoxidized soybean oil, and the thiol containing productsderived from soybean oil and epoxidized soybean oil. However, oneskilled in the art can easily adapt the procedures to the analysis ofother unsaturated esters, epoxidized unsaturated ester, and the thiolcontaining products derived from the unsaturated esters and epoxidizedunsaturated esters as described herein.

Analysis of the Polythiourethanes

The polythiourethane produced from the thiol containing esters, hydroxythiol containing esters, and cross linked thiol containing ester wereanalyzed using ASTM E1545-95A and E228-95 to provide the glasstransition temperatures and the coefficients of thermal expansion. Shorehardness of the polythiourethanes were determined using ASTM D2240-02A.The polythiourethane were also subject to a subjective analysisclassifying the polythiourethanes as hard, flexible, rubbery, rigid,tough, brittle, and other characteristics.

Applications. In addition to the uses related to fertilizers describedherein, embodiments of the present invention are useful in othernumerous applications. For example, embodiments of the invention areuseful in various polymer applications that include, but are not limitedto, as polythiourethanes, foams, adhesives, epoxy hardening agents,polyacrylates and polymethacrylate templates for paints and polyesterresins, printing ink binder polymers, alkyd resin cross-linkers, sulfurbased paint template, radiation cured polymers, mining and drillingchemicals, specialty chain transfer agents, rubber modifiers, and thelike. Because the feedstock materials are economical and readilyavailable, it is believed that embodiments of the present would beuseful in such applications and others.

The invention has been described with reference to certain preferredembodiments. However, as obvious variations thereon will become apparentto those of skill in the art, the invention is not to be limitedthereto.

TABLE 4A Example Ingredient #1 #2 #3 #4 #5 #6 B1 (g) 14.16 11.04 8.1913.38 13.38 11.91 D1 (g) — — 1.35 1.5 — D2 (g) — — — — 1.5 1.35 E (g)2.73 2.13 4.59 2.58 2.58 2.28 F1 (g) 0.15 0.09 — 0.15 0.15 0.12 C1 (b)9.96 7.74 9.87 9.39 9.39 8.34 Total coating (g) 27.00 21.00 24.00 27.0027.00 24.00 D1 overcoat (g) — 6.00 3.00 — — 3.00 Total coat (%) 2.7 2.72.7 2.7 2.7 2.7

TABLE 5A Example Ingredient #7 #8 #9 #10 B3 (g) 15.12 12.45 — — B4 (g) —— 11.01 11.01 Dl (g) 6.00 6.00 6.00 — E (g) 0 1.68 2.13 2.13 F1 (g) 0.090.06 0.12 0.12 C1 (b) 5.79 6.81 7.74 7.74 Total coating (g) 27.00 27.0027.00 21.00 D1 overcoat (g) — — — 6.00 Total coat (%) 2.7 2.7 2.7 2.7

TABLE 6A Example Ingredient #11 #12 #13 #14 B2 (g) 9.33 13.86 11.34 6.09B1 (g) — — — 3.18 D1 (g) 1.35 1.35 6.00 6.00 E (g) 2.28 — — 2.67 F1 (g)— — — — C1 (b) 11.04 11.79 9.66 9.06 Total coating (g) 24.00 27.00 27.0027.00 D1 overcoat (g) 3.00 — — — Total coat (%) 2.7 2.7 2.7 2.7

TABLE 7A Example Ingredient #15 #16 #17 B2 (g) 14.37 13.89 14.37 D1 (g)4.95 4.8 — D2 (g) — — 1.95 F2 (g) 0.12 0.12 0.12 C1 (g) — 0.90 — C2 (b)7.56 7.29 7.56 Total coating (g) 27.00 27.00 24.00 D1 overcoat (g) — —3.00 Total coat (%) 2.7 2.7 2.7

1. A controlled release fertilizer material comprising a particulateplant nutrient surrounded by a coating which is the reaction product ofa mixture comprising: (i) a first component selected from the groupconsisting of an isocyanate, an epoxy resin and mixtures thereof, and(ii) a first active hydrogen-containing compound selected from the groupconsisting of: a thiol ester composition; a hydroxy thiol estercomposition; a cross-linked thiol ester composition and mixturesthereof.
 2. The controlled release fertilizer material defined in claim1, wherein the first active hydrogen-containing compound comprises athiol ester composition comprising thiol ester molecules having anaverage of at least 1.5 ester groups per thiol ester molecule, having anaverage of at least 1.5 thiol groups per thiol ester molecule, andhaving a molar ratio of cyclic sulfides to thiol groups of less than1.5.
 3. The controlled release fertilizer material defined in claim 2,wherein the thiol ester molecules have a molar ratio of cyclic sulfidesto thiol groups ranging from 0 to 1.0.
 4. The controlled releasefertilizer material defined in claim 2, wherein the thiol estermolecules have an average ranging from 1.5 to 9 thiol groups per thiolester molecule.
 5. The controlled release fertilizer material defined inclaim 2, wherein the thiol ester molecules have a molar ratio ofcarbon-carbon double bonds to thiol groups of less than 1.5.
 6. Thecontrolled release fertilizer material defined in claim 2, wherein thethiol ester molecules have an average of greater than 2 weight percentthiol sulfur.
 7. The controlled release fertilizer material defined inclaim 2, wherein thiol ester molecules have an average ranging from 8 to10 weight percent thiol sulfur.
 8. The controlled release fertilizermaterial defined in claim 2, wherein the thiol ester molecules have anaverage of less than 30 mole percent total sulfur present as cyclicsulfides.
 9. The controlled release fertilizer material defined in claim2, wherein the thiol ester molecules have an average of less than 10mole percent total sulfur present as cyclic sulfides.
 10. The controlledrelease fertilizer material defined in claim 9, wherein greater than 40percent of thiol ester molecule total side chains contain sulfur. 11.The controlled release fertilizer material defined in claim 1, whereinthe first active hydrogen-containing compound comprises a hydroxy thiolester composition comprising hydroxy thiol ester molecules having anaverage of at least 1 ester groups per hydroxy thiol ester molecule andhaving an average of at least 1 α-hydroxy thiol groups per hydroxy thiolester molecule.
 12. The controlled release fertilizer material definedin claim 11, wherein the hydroxy thiol ester molecules have an averageranging from 1.5 to 9 α-hydroxy thiol groups per hydroxy thiol estermolecule.
 13. The controlled release fertilizer material defined inclaim 11, wherein the hydroxy thiol ester molecules have an average ofgreater than 2.5 weight percent thiol sulfur.
 14. The controlled releasefertilizer material defined in claim 11, wherein the hydroxy thiol estermolecules have an average ranging from 8 to 10 weight percent thiolsulfur.
 15. The controlled release fertilizer material defined in claim11, wherein the hydroxy thiol ester molecules have a molar ratio ofepoxide groups to the α-hydroxy thiol groups of less than
 2. 16. Thecontrolled release fertilizer material defined in claim 11, whereingreater than 40 percent of the hydroxy thiol ester molecule total sidechains contain sulfur.
 17. The controlled release fertilizer materialdefined in claim 11, wherein the hydroxy thiol ester composition issubstantially free of epoxide groups.
 18. The controlled releasefertilizer material defined in claim 1, wherein the first activehydrogen-containing compound comprises a hydroxy thiol ester compositioncomprising hydroxy thiol ester molecules having an average of at least 1ester groups per hydroxy thiol ester molecule, having an average of atleast 1 thiol groups per hydroxy thiol ester molecule, and having anaverage of at least 1 alcohol groups per hydroxy thiol ester molecule.19. The controlled release fertilizer material defined in claim 18,wherein the hydroxy thiol ester molecules have an average ranging from1.5 to 9 thiol groups per hydroxy thiol ester molecule.
 20. Thecontrolled release fertilizer material defined in claim 18, wherein thehydroxy thiol ester molecules have an average ranging from 1.5 to 9alcohol groups per hydroxy thiol ester molecule.
 21. The controlledrelease fertilizer material defined in claim 18, wherein the hydroxythiol ester molecules have an average of greater than 2.5 weight percentthiol sulfur.
 22. The controlled release fertilizer material defined inclaim 18, wherein the hydroxy thiol ester molecules have an averageranging from 8 to 10 weight percent thiol sulfur.
 23. The controlledrelease fertilizer material defined in claim 18, wherein the hydroxythiol ester molecules have a molar ratio of epoxide groups to thiolgroups of less than
 2. 24. The controlled release fertilizer materialdefined in claim 18, wherein greater than 40 percent of the hydroxythiol ester molecule total side chains contain sulfur.
 25. Thecontrolled release fertilizer material defined in claim 18, wherein thehydroxy thiol ester composition is substantially free of epoxide groups.26. The controlled release fertilizer material defined in claim 1,wherein the first active hydrogen-containing compound comprises across-linked thiol ester composition comprising thiol ester oligomershaving at least two thiol ester monomers connected by a polysulfidelinkage having a structure —S_(Q)—, wherein Q is greater than
 1. 27. Thecontrolled release fertilizer material defined in claim 26, wherein thethiol ester oligomers have at least three thiol ester monomers connectedby polysulfide linkages.
 28. The controlled release fertilizer materialdefined in claim 26, wherein the thiol ester oligomers have from 3 to 20thiol ester monomers connected by polysulfide linkages.
 29. Thecontrolled release fertilizer material defined in claim 26, wherein thecrosslinked thiol ester composition comprises thiol ester monomers andthiol ester oligomers.
 30. The controlled release fertilizer materialdefined in claim 29, wherein the thiol ester monomers and thiol esteroligomers have a total thiol sulfur content from 0.5 to 8 weightpercent.
 31. The controlled release fertilizer material defined in claim29, wherein the combined thiol ester monomers and thiol ester oligomershave an average molecular weight greater than
 2000. 32. The controlledrelease fertilizer material defined in claim 29, wherein the thiol estermonomers and thiol ester oligomers have an average molecular weight from2000 to 20,000.
 33. The controlled release fertilizer material definedin claim 29, wherein the thiol ester monomers and thiol ester oligomershave a total sulfur content ranging from 8 to 15 weight percent.
 34. Thecontrolled release fertilizer material defined in claim 1, wherein themixture further comprises a second active hydrogen-containing compounddifferent from the first active hydrogen containing compound.
 35. Thecontrolled release fertilizer material defined in claim 34, wherein thesecond active hydrogen-containing compound comprises a polyol.
 36. Thecontrolled release fertilizer material defined in claim 35, wherein thepolyol comprises from about 2 to about 12 hydroxyl moieties.
 37. Thecontrolled release fertilizer material defined in claim 35, wherein theequivalent weight of the polyol is 29-400.
 38. The controlled releasefertilizer material defined in claim 35, wherein the polyol comprises atleast one C₁₀-C₂₂ aliphatic moiety.
 39. The controlled releasefertilizer material defined in claim 1, wherein the isocyanate isselected from the group consisting of diphenylmethane diisocyanate,toluene diisocyanate, aliphatic isocyanates, derivatives thereof,polymers thereof and mixtures thereof.
 40. The controlled releasefertilizer material defined in claim 1, wherein the isocyanate comprisespolymeric diphenylmethane diisocyanate.
 41. The controlled releasefertilizer material defined in claim 1, wherein the plant nutrientcomprises a water soluble compound.
 42. The controlled releasefertilizer material defined in claim 41, wherein the water solublecompound comprises a compound containing at least one member selectedfrom the group consisting of nitrogen, phosphorus, potassium, sulfur andmixtures thereof.
 43. The controlled release fertilizer material definedin claim 1, wherein the plant nutrient comprises urea.
 44. Thecontrolled release fertilizer material defined in claim 1, wherein thefirst active hydrogen-containing compound is derived from vegetable oil.45. The controlled release fertilizer material defined in claim 1,wherein the first active hydrogen-containing compound is derived fromsoybean oil.
 46. The controlled release fertilizer material defined inclaim 1, wherein the mixture further comprises an organic additive. 47.The controlled release fertilizer material defined in claim 1, whereinthe mixture further comprises an organic wax.
 48. The controlled releasefertilizer material defined in claim 47, wherein the organic waxcomprises a drop melting point in the range of from about 30° C. toabout 120° C.
 49. The controlled release fertilizer material defined inclaim 47, wherein organic wax comprises a C₂₀₊alpha olefin wax.
 50. Thecontrolled release fertilizer material defined in claim 1, wherein thefirst component is an isocyanate.
 51. The controlled release fertilizermaterial defined in claim 1, wherein the first component is an epoxyresin.
 52. The controlled release fertilizer material defined in claim1, wherein the coating is surrounded by an overcoat layer.
 53. Thecontrolled release fertilizer material defined in claim 52, wherein theovercoat layer comprises a wax.
 54. A process for producing thecontrolled release fertilizer material defined in claim 1, the processcomprising the steps of: (a) contacting the particulate plant nutrientwith the first component and the first hydrogen-containing compound toform a coating; and (b) curing the coating to produce the controlledrelease fertilizer material.
 55. The process defined in claim 54,wherein the particulate material is agitated during Step (a).
 56. Theprocess defined in claim 54, wherein Step (a) is conducted at atemperature in the range of from about 20° C. to about 105° C.
 57. Theprocess defined in claim 54, wherein Step (a) is conducted at atemperature in the range of from about 60° C. to about 90° C.
 58. Theprocess defined in claim 54, wherein Step (a) is conducted at atemperature in the range of from about 70° C. to about 80° C.
 59. Theprocess defined in claim 54, wherein Step (a) comprises contacting theparticulate plant nutrient with a first stream comprising the firstactive hydrogen-containing compound and a second stream comprising theisocyanate, the first stream and the second stream being independent ofone another.
 60. The process defined in claim 59, wherein Step (a)comprises contacting the particulate plant nutrient simultaneously withthe first stream and the second stream.
 61. The process defined in claim59, wherein Step (a) comprises contacting the particulate plant nutrientsequentially with the first stream and the second stream.
 62. Theprocess defined in claim 59, wherein Step (a) comprises contacting theparticulate plant nutrient with the first stream followed by the secondstream.
 63. The process defined in claim 59, wherein Step (a) furthercomprises contacting the particulate plant nutrient with an organicadditive as a separate stream or in admixture with one or both of thefirst stream and the second stream.
 64. The process defined in claim 59,one or both of the first stream and the second stream comprises anorganic additive.
 65. The process defined in claim 59, wherein Step (a)further comprises contacting the particulate plant nutrient with anorganic additive as a separate stream before the first stream and/orafter the second stream or simultaneously.
 66. The process defined inclaim 54, wherein Steps (a) and (b) are repeated at least twice toproduce a controlled release fertilizer material having a plurality ofcoating layers.
 67. The process defined in claim 54, comprising thefurther step of applying a wax overcoat to the coating.